Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

PubMed Central

Vukovic, Ivana; Punzhin, Sergey; Voet, Vincent S. D.; Vukovic, Zorica; de Hosson, Jeff Th. M.; ten Brinke, Gerrit; Loos, Katja

2014-01-01

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology. PMID:24797367

Gyroid nickel nanostructures from diblock copolymer supramolecules.

PubMed

Vukovic, Ivana; Punzhin, Sergey; Voet, Vincent S D; Vukovic, Zorica; de Hosson, Jeff Th M; ten Brinke, Gerrit; Loos, Katja

2014-04-28

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, have high porosity, high surface-to-volume and strength-to-weight ratio. Unfortunately, common approaches for preparation of metallic nanostructures render materials with highly disordered architecture, which might have an adverse effect on their mechanical properties. Block copolymers have the ability to self-assemble into ordered nanostructures and can be applied as templates for the preparation of well-ordered metal nanofoams. Here we describe the application of a block copolymer-based supramolecular complex - polystyrene-block-poly(4-vinylpyridine)(pentadecylphenol) PS-b-P4VP(PDP) - as a precursor for well-ordered nickel nanofoam. The supramolecular complexes exhibit a phase behavior similar to conventional block copolymers and can self-assemble into the bicontinuous gyroid morphology with two PS networks placed in a P4VP(PDP) matrix. PDP can be dissolved in ethanol leading to the formation of a porous structure that can be backfilled with metal. Using electroless plating technique, nickel can be inserted into the template's channels. Finally, the remaining polymer can be removed via pyrolysis from the polymer/inorganic nanohybrid resulting in nanoporous nickel foam with inverse gyroid morphology.

Membranes with highly ordered straight nanopores by selective swelling of fast perpendicularly aligned block copolymers.

PubMed

Yin, Jun; Yao, Xueping; Liou, Jiun-You; Sun, Wei; Sun, Ya-Sen; Wang, Yong

2013-11-26

Membranes with uniform, straight nanopores have important applications in diverse fields, but their application is limited by the lack of efficient producing methods with high controllability. In this work, we reported on an extremely simple and efficient strategy to produce such well-defined membranes. We demonstrated that neutral solvents were capable of annealing amphiphilic block copolymer (BCP) films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) with thicknesses up to 600 nm to the perpendicular orientation within 1 min. Annealing in neutral solvents was also effective to the perpendicular alignment of block copolymers with very high molecular weights, e.g., 362 000 Da. Remarkably, simply by immersing the annealed BCP films in hot ethanol followed by drying in air, the originally dense BCP films were nondestructively converted into porous membranes containing highly ordered, straight nanopores traversing the entire thickness of the membrane (up to 1.1 μm). Grazing incident small-angle X-ray spectroscopy confirmed the hexagonal ordering of the nanopores over large areas. We found that the overflow of P2VP chains from their reservoir P2VP cylinders and the deformation of the PS matrix in the swelling process contributed to the transformation of the solid P2VP cylinders to empty straight pores. The pore diameters can be tuned by either changing the swelling temperatures or depositing thin layers of metal oxides on the preformed membranes via atomic layer deposition with a subnanometer accuracy. To demonstrate the application of the obtained porous membranes, we used them as templates and produced centimeter-scale arrays of aligned nanotubes of metal oxides with finely tunable wall thicknesses.

Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates

NASA Astrophysics Data System (ADS)

Thurn-Albrecht, T.; Schotter, J.; Kästle, G. A.; Emley, N.; Shibauchi, T.; Krusin-Elbaum, L.; Guarini, K.; Black, C. T.; Tuominen, M. T.; Russell, T. P.

2000-12-01

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 × 1011 wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.

Thin Films of Novel Linear-Dendritic Diblock Copolymers

NASA Astrophysics Data System (ADS)

Iyer, Jyotsna; Hammond, Paula

1998-03-01

A series of diblock copolymers with one linear block and one dendrimeric block have been synthesized with the objective of forming ultrathin film nanoporous membranes. Polyethyleneoxide serves as the linear hydrophilic portion of the diblock copolymer. The hyperbranched dendrimeric block consists of polyamidoamine with functional end groups. Thin films of these materials made by spin casting and the Langmuir-Blodgett techniques are being studied. The effect of the polyethylene oxide block size and the number and chemical nature of the dendrimer end group on the nature and stability of the films formed willbe discussed.

Poly-N-Isopropylacrylamide/acrylic Acid Copolymers for the Generation of Nanostructures at Mica Surfaces and as Hydrophobic Host Systems for the Porin MspA from Mycobacterium smegmatis.

PubMed

Gamage, Pubudu; Basel, Matthew T; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael; Bossmann, Stefan H

2009-09-17

The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8+/-4.4 nm for P[(NIPAM)(95.5)-co-(AA)(4.5)] (PDI (polydispersity index)=1.55) and 21.8+/-4.2 nm for P[(NIPAM)(95.3)-co-(AA)(4.7)] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)(95)-co-(AA)(2.8)-AAC(8)F(17 2.2)] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8+/-7.1 nm, with a depth of only 2 nm.

Poly-N-Isopropylacrylamide/acrylic Acid Copolymers for the Generation of Nanostructures at Mica Surfaces and as Hydrophobic Host Systems for the Porin MspA from Mycobacterium smegmatis

PubMed Central

Gamage, Pubudu; Basel, Matthew T.; Lovell, Kimberly; Pokhrel, Megh Raj; Battle, Deletria; Ito, Takashi; Pavlenok, Mikhail; Niederweis, Michael

2009-01-01

The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8±4.4 nm for P[(NIPAM)95.5-co-(AA)4.5] (PDI (polydispersity index)=1.55) and 21.8±4.2 nm for P[(NIPAM)95.3-co-(AA)4.7] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)95-co-(AA)2.8-AAC8F17 2.2] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8±7.1 nm, with a depth of only 2 nm. PMID:20161351

Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates.

PubMed

Thurn-Albrecht, T; Schotter, J; Kästle, G A; Emley, N; Shibauchi, T; Krusin-Elbaum, L; Guarini, K; Black, C T; Tuominen, M T; Russell, T P

2000-12-15

We show a simple, robust, chemical route to the fabrication of ultrahigh-density arrays of nanopores with high aspect ratios using the equilibrium self-assembled morphology of asymmetric diblock copolymers. The dimensions and lateral density of the array are determined by segmental interactions and the copolymer molecular weight. Through direct current electrodeposition, we fabricated vertical arrays of nanowires with densities in excess of 1.9 x 10(11) wires per square centimeter. We found markedly enhanced coercivities with ferromagnetic cobalt nanowires that point toward a route to ultrahigh-density storage media. The copolymer approach described is practical, parallel, compatible with current lithographic processes, and amenable to multilayered device fabrication.

Development of Active DNA Control Technique for DNA Sequencer With a Solid-state Nanopore

NASA Astrophysics Data System (ADS)

Akahori, Rena; Harada, Kunio; Goto, Yusuke; Yanagi, Itaru; Yokoi, Takahide; Oura, Takeshi; Shibahara, Masashi; Takeda, Ken-Ichi

We have developed a technique that can control the arbitrary speeds of DNA passing through a solid-state nanopore of a DNA sequencer. For this active DNA control technique, we used a DNA-immobilized Si probe, larger than the membrane with a nanopore, and used a piezoelectric actuator and stepper motor to drive the probe. This probe enables a user to adjust the relative position between the nanopore and DNA immobilized on the probe without the need for precise lateral control. In this presentation, we demonstrate how DNA (block copolymer ([(dT)25-(dC)25-(dA)50]m)), immobilized on the probe, slid through a nanopore and was pulled out using the active DNA control technique. As the DNA-immobilized probe was being pulled out, we obtained various ion-current signal levels corresponding to the number of different nucleotides in a single strand of DNA.

Nanoporous capsules of block co-polymers of [(MeO-PEG-NH)-b-(L-GluA)]-PCL for the controlled release of anticancer drugs for therapeutic applications.

PubMed

Amgoth, Chander; Dharmapuri, Gangappa; Kalle, Arunasree M; Paik, Pradip

2016-03-29

Herein, new nanoporous capsules of the block co-polymers of MeO-PEG-NH-(L-GluA)10 and polycaprolactone (PCL) have been synthesized through a surfactant-free cost-effective self-assembled soft-templating approach for the controlled release of drugs and for therapeutic applications. The nanoporous polymer capsules are designed to be biocompatible and are capable of encapsulating anticancer drugs (e.g., doxorubicin hydrochloride (DOX) and imatinib mesylate (ITM)) with a high extent (∼279 and ∼480 ng μg(-1), respectively). We have developed a nanoformulation of porous MeO-PEG-NH-(L-GluA)10-PCL capsules with DOX and ITM. The porous polymer nanoformulations have been programmed in terms of the release of anticancer drugs with a desired dose to treat the leukemia (K562) and human carcinoma cells (HepG2) in vitro and show promising IC50 values with a very high mortality of cancer cells (up to ∼96.6%). Our nanoformulation arrests the cell divisions due to 'cellular scenescence' and kills the cancer cells specifically. The present findings could enrich the effectiveness of idiosyncratic nanoporous polymer capsules for use in various other nanomedicinal and biomedical applications, such as for killing cancer cells, immune therapy, and gene delivery.

Nanoporous capsules of block co-polymers of [(MeO-PEG-NH)-b-(L-GluA)]-PCL for the controlled release of anticancer drugs for therapeutic applications

NASA Astrophysics Data System (ADS)

Amgoth, Chander; Dharmapuri, Gangappa; Kalle, Arunasree M.; Paik, Pradip

2016-03-01

Herein, new nanoporous capsules of the block co-polymers of MeO-PEG-NH-(L-GluA)10 and polycaprolactone (PCL) have been synthesized through a surfactant-free cost-effective self-assembled soft-templating approach for the controlled release of drugs and for therapeutic applications. The nanoporous polymer capsules are designed to be biocompatible and are capable of encapsulating anticancer drugs (e.g., doxorubicin hydrochloride (DOX) and imatinib mesylate (ITM)) with a high extent (˜279 and ˜480 ng μg-1, respectively). We have developed a nanoformulation of porous MeO-PEG-NH-(L-GluA)10-PCL capsules with DOX and ITM. The porous polymer nanoformulations have been programmed in terms of the release of anticancer drugs with a desired dose to treat the leukemia (K562) and human carcinoma cells (HepG2) in vitro and show promising IC50 values with a very high mortality of cancer cells (up to ˜96.6%). Our nanoformulation arrests the cell divisions due to ‘cellular scenescence’ and kills the cancer cells specifically. The present findings could enrich the effectiveness of idiosyncratic nanoporous polymer capsules for use in various other nanomedicinal and biomedical applications, such as for killing cancer cells, immune therapy, and gene delivery.

Molecular transport through nanoporous silicon nitride membranes produced from self-assembling block copolymers.

PubMed

Montagne, Franck; Blondiaux, Nicolas; Bojko, Alexandre; Pugin, Raphaël

2012-09-28

To achieve fast and selective molecular filtration, membrane materials must ideally exhibit a thin porous skin and a high density of pores with a narrow size distribution. Here, we report the fabrication of nanoporous silicon nitride membranes (NSiMs) at the full wafer scale using a versatile process combining block copolymer (BCP) self-assembly and conventional photolithography/etching techniques. In our method, self-assembled BCP micelles are used as templates for creating sub-100 nm nanopores in a thin low-stress silicon nitride layer, which is then released from the underlying silicon wafer by etching. The process yields 100 nm thick free-standing NSiMs of various lateral dimensions (up to a few mm(2)). We show that the membranes exhibit a high pore density, while still retaining excellent mechanical strength. Permeation experiments reveal that the molecular transport rate across NSiMs is up to 16-fold faster than that of commercial polymeric membranes. Moreover, using dextran molecules of various molecular weights, we also demonstrate that size-based separation can be achieved with a very good selectivity. These new silicon nanosieves offer a relevant technological alternative to commercially available ultra- and microfiltration membranes for conducting high resolution biomolecular separations at small scales.

ABC triblock copolymer vesicles with mesh-like morphology.

PubMed

Zhao, Wei; Chen, Dian; Hu, Yunxia; Grason, Gregory M; Russell, Thomas P

2011-01-25

Polymer vesicles made from poly(isoprene-b-styrene-b-2-vinyl pyridine) (PI-b-PS-b-P2VP) triblock copolymer confined within the nanopores of an anodic aluminum oxide (AAO) membrane are studied. It was found that these vesicles have well-defined, nanoscopic size, and complex microphase-separated hydrophobic membranes, comprised of the PS and PI blocks, while the coronas are formed by the P2VP block. Vesicle formation was tracked using both transmission and scanning electron microscopy. A mesh-like morphology formed in the membrane at a well-defined composition of the three blocks that can be tuned by changing the copolymer composition. The nanoscale confinement, copolymer composition, and subtle molecular interactions contribute to the generation of these vesicles with such unusual morphologies.

Silicon crystallization in nanodot arrays organized by block copolymer lithography

NASA Astrophysics Data System (ADS)

Perego, Michele; Andreozzi, Andrea; Seguini, Gabriele; Schamm-Chardon, Sylvie; Castro, Celia; BenAssayag, Gerard

2014-12-01

Asymmetric polystyrene- b-polymethylmethacrylate (PS- b-PMMA) block copolymers are used to fabricate nanoporous PS templates with different pore diameter depending on the specific substrate neutralization protocol. The resulting polymeric templates are used as masks for the subsequent deposition of a thin ( h = 5 nm) amorphous Si layer by electron beam evaporation. After removal of the polymeric film and of the silicon excess, well-defined hexagonally packed amorphous Si nanodots are formed on the substrate. Their average diameter ( d < 20 nm), density (1.2 × 1011 cm-2), and lateral distribution closely mimic the original nanoporous template. Upon capping with SiO2 and high temperature annealing (1050 °C, N2), each amorphous Si nanodot rearranges in agglomerates of Si nanocrystals ( d < 4 nm). The average diameter and shape of these Si nanocrystals strongly depend on the size of the initial Si nanodot.

Biomimetic block copolymer particles with gated nanopores and ultrahigh protein sorption capacity

NASA Astrophysics Data System (ADS)

Yu, Haizhou; Qiu, Xiaoyan; Nunes, Suzana P.; Peinemann, Klaus-Viktor

2014-06-01

The design of micro- or nanoparticles that can encapsulate sensitive molecules such as drugs, hormones, proteins or peptides is of increasing importance for applications in biotechnology and medicine. Examples are micelles, liposomes and vesicles. The tiny and, in most cases, hollow spheres are used as vehicles for transport and controlled administration of pharmaceutical drugs or nutrients. Here we report a simple strategy to fabricate microspheres by block copolymer self-assembly. The microsphere particles have monodispersed nanopores that can act as pH-responsive gates. They contain a highly porous internal structure, which is analogous to the Schwarz P structure. The internal porosity of the particles contributes to their high sorption capacity and sustained release behaviour. We successfully separated similarly sized proteins using these particles. The ease of particle fabrication by macrophase separation and self-assembly, and the robustness of the particles makes them ideal for sorption, separation, transport and sustained delivery of pharmaceutical substances.

Construction of a thermoresponsive magnetic porous polymer membrane enzyme reactor for glutaminase kinetics study.

PubMed

Zhao, Liping; Qiao, Juan; Moon, Meyong Hee; Qi, Li

2018-06-16

Fabrication of polymer membranes with nanopores and a confinement effect toward enzyme immobilization has been an enabling endeavor. In the work reported here, an enzyme reactor based on a thermoresponsive magnetic porous block copolymer membrane was designed and constructed. Reversible addition-fragmentation chain transfer polymerization was used to synthesize the block copolymer, poly(maleic anhydride-styrene-N-isopropylacrylamide), with poly(N-isopropylacrylamide) as the thermoresponsive moiety. The self-assembly property of the block copolymer was used for preparation of magnetic porous thin film matrices with iron oxide nanoparticles. By covalent bonding of glutaminase onto the surface of the membrane matrices and changing the temperature to tune the nanopore size, we observed enhanced enzymolysis efficiency due to the confinement effect. The apparent Michaelis-Menten constant and the maximum rate of the enzyme reactor were determined (K m = 32.3 mM, V max = 33.3 mM min -1 ) by a chiral ligand exchange capillary electrochromatography protocol with L-glutamine as the substrate. Compared with free glutaminase in solution, the proposed enzyme reactor exhibits higher enzymolysis efficiency, greater stability, and greater reusability. Furthermore, the enzyme reactor was applied for a glutaminase kinetics study. The tailored pore sizes and the thermoresponsive property of the block copolymer result in the designed porous membrane based enzyme reactor having great potential for high enzymolysis performance. Graphical abstract ᅟ.

Substrate effect on nanoporous structure of silica wires by channel-confined self-assembly of block-copolymer and sol-gel precursors

DOE PAGES

Hu, Michael Z.; Lai, Peng

2015-09-22

Nanoporous silica wires of various wire diameters were developed by space-confined molecular self-assembly of triblock copolymer ethylene/propylene/ethylene (P123) and silica alkoxide precursor (tetraethylorthosilicate, TEOS). Two distinctive hard-templating substrates, anodized aluminum oxide (AAO) and track-etched polycarbonate (EPC), with channel diameters in the range between 10 nm and 200 nm were employed for space-confinement of soft molecular self-assembly driven by the block-copolymer microphase separation. It was observed in the scanning and transmission electron microscope (STEM) studies that the substrate geometry and material characteristics had pronounced effects on the structure and morphology of the silica nanowires. A substrate wall effect was proposed tomore » explain the ordering and orientation of the intra-wire mesostructure. Circular and spiral nanostructures were found only in wires formed in AAO substrate, not in EPC. Pore-size differences and distinctive wall morphologies of the nanowires relating to the substrates were discussed. It was shown that the material and channel wall characteristics of different substrates play key roles in the ordering and morphology of the intra-wire nanostructures.« less

Controlling pore morphology and properties of nanoporous silica films using the different architecture PS-b-P2VP as a template.

PubMed

Yu, Yang-Yen; Chien, Wen-Chen; Chen, Shih-Ting

2010-07-01

Nanoporous silica films were prepared through the templating of amphiphilic block copolymer, poly(styrene-2-vinyl pyridine) (PS-b-P2VP), and monodispersed colloidal silica nanoparticles. The experimental and theoretical studies suggested that the intermolecular hydrogen bonding existes between the colloidal silica nanoparticles and PS-b-P2VP. The effects of the loading ratio and P2VP chain length on the morphology and properties of the prepared nanoporous silica films were investigated. TEM and AFM studies showed that the uniform pore size could be achieved and the pore size increased with increasing porogen loading. The refractive index and dielectric constant of the prepared nanoporous films decreased with an increase in PS-b-P2VP loading. On the other hand, the porosity increased with an increasing PS-b-P2VP loading. This study demonstrated a methodology to control pore morphology and properties of the nanoporous silica films through the templating of PS-b-P2VP.

Phosphorene-directed self-assembly of asymmetric PS-b-PMMA block copolymer for perpendicularly-oriented sub-10 nm PS nanopore arrays

NASA Astrophysics Data System (ADS)

Zhang, Ziming; Zheng, Lu; Khurram, Muhammad; Yan, Qingfeng

2017-10-01

Few-layer black phosphorus, also known as phosphorene, is a new two-dimensional material which is of enormous interest for applications, mainly in electronics and optoelectronics. Herein, we for the first time employ phosphorene for directing the self-assembly of asymmetric polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymer (BCP) thin film to form the perpendicular orientation of sub-10 nm PS nanopore arrays in a hexagonal fashion normal to the interface. We experimentally demonstrate that none of the PS and PMMA blocks exhibit preferential affinity to the phosphorene-modified surface. Furthermore, the perpendicularly-oriented PS nanostructures almost stay unchanged with the variation of number of layers of few-layer phosphorene nanoflakes between 15-30 layers. Differing from the neutral polymer brushes which are widely used for chemical modification of the silicon substrate, phosphorene provides a novel physical way to control the interfacial interactions between the asymmetric PS-b-PMMA BCP thin film and the silicon substrate. Based on our results, it is possible to build a new scheme for producing sub-10 nm PS nanopore arrays oriented perpendicularly to the few-layer phosphorene nanoflakes. Furthermore, the nanostructural microdomains could serve as a promising nanolithography template for surface patterning of phosphorene nanoflakes.

The influence of polarity of additive molecules on micelle structures of polystyrene-block-poly(4-vinylpyridine) in the fabrication of nano-porous templates.

PubMed

Chua, Kee Sze; Koh, Ai Peng; Lam, Yeng Ming

2010-11-01

Block copolymers are useful for in situ synthesis of nanoparticles as well as producing nanoporous templates. As such, the effects of precursors on the block copolymer micelle structure is important. In this study, we investigate the effects of polarity of molecules introduced into block copolymer micelle cores on the micelle structure. The molecular dipole moment of the additive molecules has been evaluated and their effects on the block copolymer micelles investigated using light scattering spectroscopy, small-angle X-ray scattering, transmission electron microscopy and atomic force microscopy. The molecule with the largest dipole moment resulted in spherical structures with a polydispersity of less than 0.06 in a fully translational diffusion system. Surprisingly, the less polar additive molecules produced elongated micelles and the aspect ratio increases with decreasing polarity. The change in structure from spherical to elongated structure was attributed to P4VP chain extension, where compounds with polarity most similar to P4VP induce the most chain extension. The second virial coefficients of the solutions with elongated micelles are lower than that for spherical micelle systems by up to one order in magnitude, indicating a strong tendency for micelles to coalesce. On rinsing the spin-cast films, pores were obtained from spherical micelles and ridges from elongated micelles, suggesting a viable alternative for morphology modification using mild conditions where external annealing treatments to the film are not preferred. The knowledge of polarity effects of additive molecules on micelle structure has wider implications for supramolecular block copolymer systems where, depending on the application requirements, changes to the shape of the micelle structure can be induced or avoided. Copyright 2010 Elsevier Inc. All rights reserved.

Preparation of Mesoporous Ceramics from Polymer Nanotubes

NASA Astrophysics Data System (ADS)

Chen, Dian; Park, Soojin; Chen, Jiun-Tai; Redston, Emily; Russell, Thomas

2009-03-01

Poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) nanotubes were prepared by placing polymer solution into the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. The PS-b-P4VP nanotubes within the AAO membranes were exposed to tetrahydrofuran vapor to produce uniform spherical micelles along the tube. The tubes were removed from the membranes, then suspended in ethylene glycol, a preferential solvent for P4VP. At 95^ oC, near the glass transition temperature (Tg) of PS, nanotubes with uniform nanopores were obtained by a reconstruction of the nanotubes. As the temperature was increased, mesoporous polymer structures were obtained. Tetraethyl orthosilicate or titanium tetraethoxide, ceramic precursors, were introduced into the 4VP microdomains. After exposure to an oxygen plasma or high temperature, the copolymer was removed and the precursor converted to a mesoporous ceramic. This process offers a simple route for the fabrication of tunable mesoporous ceramic or metallic structures by changing molecular weight of copolymers.

Linker-based control of electron propagation through ferrocene moieties covalently anchored onto insulator-based nanopores derived from a polystyrene-poly(methylmethacrylate) diblock copolymer.

PubMed

Li, Feng; Pandey, Bipin; Ito, Takashi

2012-12-04

This paper reports the effects of linker length on electron propagation through ferrocene moieties covalently anchored onto insulator-based cylindrical nanopores derived from a cylinder-forming polystyrene-poly(methylmethacrylate) diblock copolymer. These nanopores (24 nm in diameter, 30 nm long) aligned perpendicular to an underlying gold electrode were modified via esterification of their surface COOH groups with OH-terminated ferrocene derivatives having different alkyl linkers (FcCO(CH(2))(n)OH; n = 2, 5, 15). Cyclic voltammograms were measured in 0.1 M NaBF(4) at different scan rates to assess the efficiency of electron propagation through the ferrocene moieties. The redox peaks of the anchored ferrocenes were observed at nanoporous films decorated with FcCO(CH(2))(15)OH and FcCO(CH(2))(5)OH, but not at those with FcCO(CH(2))(2)OH. Importantly, the higher electron propagation efficiency was observed in the use of the longer linker, as shown by the apparent diffusion coefficients (ca. 10(-12) cm(2)/s for n = 15; ca. 10(-13) cm(2)/s for n = 5; no electron propagation for n = 2). The observed electron propagation resulted from electron hopping across relatively large spacing that was controlled by the motion of anchored redox sites (bounded diffusion). The longer linker led to the larger physical displacement range of anchored ferrocene moieties, facilitating the approach of the adjacent ferrocene moieties within a distance required for electron self-exchange reaction. The linker-based control of redox-involved electron propagation on nanostructured, insulating surfaces will provide a means for designing novel molecular electronics and electrochemical sensors.

Fabrication of metallized nanoporous films from the self-assembly of a block copolymer and homopolymer mixture.

PubMed

Li, Xue; Zhao, Shuying; Zhang, Shuxiang; Kim, Dong Ha; Knoll, Wolfgang

2007-06-19

Inorganic compound HAuCl4, which can form a complex with pyridine, is introduced into a poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) block copolymer/poly(methyl methacrylate) (PMMA) homopolymer mixture. The orientation of the cylindrical microdomains formed by the P2VP block, PMMA, and HAuCl4 normal to the substrate surface can be generated via cooperative self-assembly of the mixture. Selective removal of the homopolymer can lead to porous nanostructures containing metal components in P2VP domains, which have a novel photoluminescence property.

Method for synthesizing carbon nanotubes

DOEpatents

Fan, Hongyou

2012-09-04

A method for preparing a precursor solution for synthesis of carbon nanomaterials, where a polar solvent is added to at least one block copolymer and at least one carbohydrate compound, and the precursor solution is processed using a self-assembly process and subsequent heating to form nanoporous carbon films, porous carbon nanotubes, and porous carbon nanoparticles.

Gas Transport Selectivity of Ultrathin, Nanoporous, Inorganic Membranes Made from Block Copolymer Templates

DOE PAGES

Greil, Stefanie; Rahman, Atikur; Liu, Mingzhao; ...

2017-10-10

Here, we report the fabrication of ultrathin, nanoporous silicon nitride membranes made from templates of regular, nanoscale features in self-assembled block copolymer thin films. The inorganic membranes feature thicknesses less than 50 nm and volume porosities over 30%, with straight-through pores that offer high throughout for gas transport and separation applications. As fabricated, the pores are uniformly around 20 nm in diameter, but they can be controllably and continuously tuned to single-digit nanometer dimensions by atomic layer deposition of conformal coatings. A deviation from expected Knudsen diffusion is revealed for transport characteristics of saturated vapors of organic solvents across themore » membrane, which becomes more significant for membranes of smaller pores. We attribute this to capillary condensation of saturated vapors within membrane pores, which reduces membrane throughput by over 1 order of magnitude but significantly improves the membrane’s selectivity. Between vapors of acetone and ethyl acetate, we measure selectivities as high as 7:1 at ambient pressure and temperature, 4 times more than the Knudsen selectivity.« less

Gas Transport Selectivity of Ultrathin, Nanoporous, Inorganic Membranes Made from Block Copolymer Templates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greil, Stefanie; Rahman, Atikur; Liu, Mingzhao

Here, we report the fabrication of ultrathin, nanoporous silicon nitride membranes made from templates of regular, nanoscale features in self-assembled block copolymer thin films. The inorganic membranes feature thicknesses less than 50 nm and volume porosities over 30%, with straight-through pores that offer high throughout for gas transport and separation applications. As fabricated, the pores are uniformly around 20 nm in diameter, but they can be controllably and continuously tuned to single-digit nanometer dimensions by atomic layer deposition of conformal coatings. A deviation from expected Knudsen diffusion is revealed for transport characteristics of saturated vapors of organic solvents across themore » membrane, which becomes more significant for membranes of smaller pores. We attribute this to capillary condensation of saturated vapors within membrane pores, which reduces membrane throughput by over 1 order of magnitude but significantly improves the membrane’s selectivity. Between vapors of acetone and ethyl acetate, we measure selectivities as high as 7:1 at ambient pressure and temperature, 4 times more than the Knudsen selectivity.« less

Elucidation of the Structure Formation of Polymer-Conjugated Proteins in Solution and Block Copolymer Templates

NASA Astrophysics Data System (ADS)

Ferebee, Rachel L.

The broader technical objective of this work is to contribute to the development of enzyme-functionalized nanoporous membranes that can function as autonomous and target selective dynamic separators. The scientific objective of the research performed within this thesis is to elucidate the parameters that control the mixing of proteins in organic host materials and in block copolymers templates in particular. A "biomimetic" membrane system that uses enzymes to selectively neutralize targets and trigger a change in permeability of nanopores lined with a pH-responsive polymer has been fabricated and characterized. Mechanical and functional stability, as well as scalability, have been demonstrated for this system. Additional research has focused on the role of polymeric ligands on the solubility characteristics of the model protein, Bovine Serum Albumin (BSA). For this purpose BSA was conjugated with poly(ethylene glycol) (PEG) ligands of varied degree of polymerization and grafting density. Combined static and dynamic light scattering was used (in conjunction with MALDI-TOF) to determine the second virial coefficient in PBS solutions. At a given mass fraction PEG or average number of grafts, the solubility of BSA-PEG conjugates is found to increase with the degree of polymerization of conjugated PEG. This result informs the synthesis of protein-conjugate systems that are optimized for the fabrication of block copolymer blend materials with maximum protein loading. Blends of BSA-PEG conjugates and block copolymer (BCP) matrices were fabricated to evaluate the dispersion morphology and solubility limits in a model system. Electron microscopy was used to evaluate the changes in lamellar spacing with increased filling fraction of BSA-PEG conjugates.

New self-assembly strategies for next generation lithography

NASA Astrophysics Data System (ADS)

Schwartz, Evan L.; Bosworth, Joan K.; Paik, Marvin Y.; Ober, Christopher K.

2010-04-01

Future demands of the semiconductor industry call for robust patterning strategies for critical dimensions below twenty nanometers. The self assembly of block copolymers stands out as a promising, potentially lower cost alternative to other technologies such as e-beam or nanoimprint lithography. One approach is to use block copolymers that can be lithographically patterned by incorporating a negative-tone photoresist as the majority (matrix) phase of the block copolymer, paired with photoacid generator and a crosslinker moiety. In this system, poly(α-methylstyrene-block-hydroxystyrene)(PαMS-b-PHOST), the block copolymer is spin-coated as a thin film, processed to a desired microdomain orientation with long-range order, and then photopatterned. Therefore, selfassembly of the block copolymer only occurs in select areas due to the crosslinking of the matrix phase, and the minority phase polymer can be removed to produce a nanoporous template. Using bulk TEM analysis, we demonstrate how the critical dimension of this block copolymer is shown to scale with polymer molecular weight using a simple power law relation. Enthalpic interactions such as hydrogen bonding are used to blend inorganic additives in order to enhance the etch resistance of the PHOST block. We demonstrate how lithographically patternable block copolymers might fit in to future processing strategies to produce etch-resistant self-assembled features at length scales impossible with conventional lithography.

Synthetic Design of Polysulfone Membranes: Morphological Effect on Property and Performance in Flow Batteries

NASA Astrophysics Data System (ADS)

Gindt, Brandon

This dissertation outlines a novel path towards improved understanding and function of proton exchange membranes (PEMs) for redox flow batteries, a large-scale battery storage device. This research uses synthetic methods and nanotechnology through two different approaches to prepare tailored polymer membranes: 1) Ion exchange membranes with enhanced chemical structures to promote membrane morphology on the nano-scale were prepared. Specifically, functional polysulfones (PSUs) were synthesized from different pre-sulfonated monomers. These PSUs have controlled placement and content of unique sulfonic acid moieties. PEMs were fabricated and characterized. The new PEMs showed desirable physical properties and performance in a vanadium redox flow battery (VRFB) cell. 2) Nanoporous PSU membranes were fabricated via post-hydrolysis of polylactide (PLA) from PLA-PSU-PLA triblock copolymer membranes. The controlled morphology and pore size of the resulting nanoporous membranes were evaluated by different microscopy and scattering techniques to understand structure-property relationships. Further, the resulting nanopore surface was chemically modified with sulfonic acid moieties. Membranes were analyzed and evaluated as separators for a VRFB. The chemically modified nanoporous PEMs exhibited unique behavior with respect to their ion conductivity when exposed to solutions of increasing acid concentration. In addition, the hierarchical micro-nanoporous membranes developed further showed promising structure and properties.

Graphene Nanopore Support System for Simultaneous High-Resolution AFM Imaging and Conductance Measurements

PubMed Central

2015-01-01

Accurately defining the nanoporous structure and sensing the ionic flow across nanoscale pores in thin films and membranes has a wide range of applications, including characterization of biological ion channels and receptors, DNA sequencing, molecule separation by nanoparticle films, sensing by block co-polymers films, and catalysis through metal–organic frameworks. Ionic conductance through nanopores is often regulated by their 3D structures, a relationship that can be accurately determined only by their simultaneous measurements. However, defining their structure–function relationships directly by any existing techniques is still not possible. Atomic force microscopy (AFM) can image the structures of these pores at high resolution in an aqueous environment, and electrophysiological techniques can measure ion flow through individual nanoscale pores. Combining these techniques is limited by the lack of nanoscale interfaces. We have designed a graphene-based single-nanopore support (∼5 nm thick with ∼20 nm pore diameter) and have integrated AFM imaging and ionic conductance recording using our newly designed double-chamber recording system to study an overlaid thin film. The functionality of this integrated system is demonstrated by electrical recording (<10 pS conductance) of suspended lipid bilayers spanning a nanopore and simultaneous AFM imaging of the bilayer. PMID:24581087

Mesoporous Polymer Frameworks from End-Reactive Bottlebrush Copolymers

DOE PAGES

Altay, Esra; Nykypanchuk, Dmytro; Rzayev, Javid

2017-08-07

Reticulated nanoporous materials generated by versatile molecular framework approaches are limited to pore dimensions on the scale of the utilized rigid molecular building blocks (<5 nm). The inherent flexibility of linear polymers precludes their utilization as long framework connectors for the extension of this strategy to larger length scales. We report a method for the fabrication of mesoporous frameworks by using bottlebrush copolymers with reactive end blocks serving as rigid macromolecular interconnectors with directional reactivity. End-reactive bottlebrush copolymers with pendant alkene functionalities were synthesized by a combination of controlled radical polymerization and polymer modification protocols. Ru-catalyzed cross-metathesis cross-linking of bottlebrushmore » copolymers with two reactive end blocks resulted in the formation of polymer frameworks where isolated cross-linked domains were interconnected with bottlebrush copolymer bridges. The resulting materials were characterized by a continuous network pore structure with average pore sizes of 9–50 nm, conveniently tunable by the length of the utilized bottlebrush copolymer building blocks. As a result, the materials fabrication strategy described in this work expands the length scale of molecular framework materials and provides access to mesoporous polymers with a molecularly tunable reticulated pore structure without the need for templating, sacrificial component etching, or supercritical fluid drying.« less

Interaction chromatography for characterization and large-scale fractionation of chemically heterogeneous copolymers

NASA Astrophysics Data System (ADS)

Han, Junwon

The remarkable development of polymer synthesis techniques to make complex polymers with controlled chain architectures has inevitably demanded the advancement of polymer characterization tools to analyze the molecular dispersity in polymeric materials beyond size exclusion chromatography (SEC). In particular, man-made synthetic copolymers that consist of more than one monomer type are disperse mixtures of polymer chains that have distributions in terms of both chemical heterogeneity and chain length (molar mass). While the molecular weight distribution has been quite reliably estimated by the SEC, it is still challenging to properly characterize the chemical composition distribution in the copolymers. Here, I have developed and applied adsorption-based interaction chromatography (IC) techniques as a promising tool to characterize and fractionate polystyrene-based block, random and branched copolymers in terms of their chemical heterogeneity. The first part of this thesis is focused on the adsorption-desorption based purification of PS-b-PMMA diblock copolymers using nanoporous silica. The liquid chromatography analysis and large scale purification are discussed for the PS-b-PMMA block copolymers that have been synthesized by sequential anionic polymerization. SEC and IC are compared to critically analyze the contents of PS homopolymers in the as-synthesized block copolymers. In addition, I have developed an IC technique to provide faster and more reliable information on the chemical heterogeneity in the as-synthesized block copolymers. Finally, a large scale (multi-gram) separation technique is developed to obtain "homopolymer-free" block copolymers via a simple chromatographic filtration technique. By taking advantage of the large specific surface area of nanoporous silica (≈300m 2/g), large scale purification of neat PS-b-PMMA has successfully been achieved by controlling adsorption and desorption of the block copolymers on the silica gel surface using a gravity column. The second part of this thesis is focused on the liquid chromatography analysis and fractionation of RAFT-polymerized PS-b -PMMA diblock copolymers and AFM studies. In this study, PS- b-PMMA block copolymers were synthesized by a RAFT free radical polymerization process---the PMMA block with a phenyldithiobenzoate end group was synthesized first. The contents of unreacted PS and PMMA homopolymers in as-synthesized PS-b-PMMA block copolymers were quantitatively analyzed by solvent gradient interaction chromatography (SGIC) technique employing bare silica and C18-bonded silica columns, respectively. In addition, by 2-dimensional large-scale IC fractionation method, atomic force microscopy (AFM) study of these fractionated samples revealed various morphologies with respect to the chemical composition of each fraction. The third part of this thesis is to analyze random copolymers with tunable monomer sequence distributions using interaction chromatography. Here, IC was used for characterizing the composition and monomer sequence distribution in statistical copolymers of poly(styrene-co-4-bromostyrene) (PBrxS). The PBrS copolymers were synthesized by the bromination of monodisperse polystyrenes; the degree of bromination (x) and the sequence distribution were adjusted by varying the bromination time and the solvent quality, respectively. Both normal-phase (bare silica) and reversed-phase (C18-bonded silica) columns were used at different combinations of solvents and non-solvents to monitor the content of the 4-bromostyrene units in the copolymer and their average monomer sequence distribution. The fourth part of this thesis is to analyze and fractionate highly branched polymers such as dendronized polymers and star-shaped homo and copolymers. I have developed an interaction chromatography technique to separate polymers with nonlinear chain architecture. Specifically, the IC technique has been used to separate dendronized polymers and PS-based highly branched copolymers and to ultimately obtain well-defined dendronized or branched copolymers with a low polydispersity. The effects of excess arm-polymers on (1) the micellar self-assembly of dendronized polymers and (2) the regularity of the pore morphology in the low-k applications by the sol-gel process have been studied.

Reversible switch between the nanoporous and the nonporous state of amphiphilic block copolymer films regulated by selective swelling.

PubMed

Yan, Nina; Wang, Yong

2015-09-21

Switchable nanoporous films, which can repeatedly alternate their porosities, are of great interest in a diversity of fields. Currently these intelligent materials are mostly based on polyelectrolytes and their porosities can change only in relatively narrow ranges, typically under wet conditions, severely limiting their applications. Here we develop a new system, which is capable of reversibly switching between a highly porous state and a nonporous state dozens of times regulated simply by exposure to selective solvents. In this system nanopores are created or reversibly eliminated in films of a block copolymer, polystyrene-block-poly(2-vinyl pyridine) (PS-b-P2VP), by exposing the films to P2VP-selective or PS-selective solvents, respectively. The mechanism of the switch is based on the selective swelling of the constituent blocks in corresponding solvents, which is a nondestructive and easily controllable process enabling the repeatable and ample switch between the open and the closed state. Systematic microscopic and ellipsometric characterization methods are performed to elucidate the pore-closing course induced by nonsolvents and the cycling between the pore-open and the pore-closed state up to 20 times. The affinity of the solvent for PS blocks is found to play a dominating role in determining the pore-closing process and the porosities of the pore-open films increase with the cycling numbers as a result of loose packing conditions of the polymer chains. We finally demonstrate the potential applications of these films as intelligent antireflection coatings and drug carriers.

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

DOE PAGES

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

2016-11-03

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

Low-Dielectric Constant Polyimide Nanoporous Films: Synthesis and Properties

NASA Astrophysics Data System (ADS)

Mehdipour-Ataei, S.; Rahimi, A.; Saidi, S.

2007-08-01

Synthesis of high temperature polyimide foams with pore sizes in the nanometer range was developed. Foams were prepared by casting graft copolymers comprising a thermally stable block as the matrix and a thermally labile material as the dispersed phase. Polyimides derived from pyromellitic dianhydride with new diamines (4BAP and BAN) were used as the matrix material and functionalized poly(propylene glycol) oligomers were used as a thermally labile constituent. Upon thermal treatment the labile blocks were subsequently removed leaving pores with the size and shape of the original copolymer morphology. The polyimides and foamed polyimides were characterized by some conventional methods including FTIR, H-NMR, DSC, TGA, SEM, TEM, and dielectric constant.

Model A: High-Temperature Tribometer

DTIC Science & Technology

1992-02-01

spring loaded collet which grips the pin. In previous machines Inconel 625 collets and sleeves with 450 contact angles were used without collet...Triboeter, high temperature, friction, wear 11 1 08__ 19 ABSTRACT (Continue on revere if necewry and identify by blck number) A high temperature...tribometer has been specifically designed and fabricated to accurately measure, in real time, friction and wear characteristics of materials at temperatures

Nanopatterned carbon films with engineered morphology by direct carbonization of UV-stabilized block copolymer films.

PubMed

Wang, Yong; Liu, Jinquan; Christiansen, Silke; Kim, Dong Ha; Gösele, Ulrich; Steinhart, Martin

2008-11-01

Nanopatterned thin carbon films were prepared by direct and expeditious carbonization of the block copolymer polystyrene- block-poly(2-vinylpyridine) (PS- b-P2VP) without the necessity of slow heating to the process temperature and of addition of further carbon precursors. Carbonaceous films having an ordered "dots-on-film" surface topology were obtained from reverse micelle monolayers. The regular nanoporous morphology of PS- b-P2VP films obtained by subjecting reverse micelle monolayers to swelling-induced surface reconstruction could likewise be transferred to carbon films thus characterized by ordered nanopit arrays. Stabilization of PS- b-P2VP by UV irradiation and the concurrent carbonization of both blocks were key to the conservation of the film topography. The approach reported here may enable the realization of a broad range of nanoscaled architectures for carbonaceous materials using a block copolymer ideally suited as a template because of the pronounced repulsion between its blocks and its capability to form highly ordered microdomain structures.

Surface Attachment of Gold Nanoparticles Guided by Block Copolymer Micellar Films and Its Application in Silicon Etching

PubMed Central

Wei, Mingjie; Wang, Yong

2015-01-01

Patterning metallic nanoparticles on substrate surfaces is important in a number of applications. However, it remains challenging to fabricate such patterned nanoparticles with easily controlled structural parameters, including particle sizes and densities, from simple methods. We report on a new route to directly pattern pre-formed gold nanoparticles with different diameters on block copolymer micellar monolayers coated on silicon substrates. Due to the synergetic effect of complexation and electrostatic interactions between the micellar cores and the gold particles, incubating the copolymer-coated silicon in a gold nanoparticles suspension leads to a monolayer of gold particles attached on the coated silicon. The intermediate micellar film was then removed using oxygen plasma treatment, allowing the direct contact of the gold particles with the Si substrate. We further demonstrate that the gold nanoparticles can serve as catalysts for the localized etching of the silicon substrate, resulting in nanoporous Si with a top layer of straight pores. PMID:28793407

Multicompartmental Microcapsules from Star Copolymer Micelles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Ikjun; Malak, Sidney T.; Xu, Weinan

2013-02-26

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into themore » LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.« less

Controlling the Morphology of Side Chain Liquid Crystalline Block Copolymer Thin Films through Variations in Liquid Crystalline Content

PubMed Central

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T.

2009-01-01

In this paper we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the inter-material dividing surface (IMDS). By manipulating the strength of these interactions the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nano-patterning applications without manipulation of the surface chemistry or the application of external fields. PMID:18763835

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content.

PubMed

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T

2008-10-01

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface. By manipulating the strength of these interactions, the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nanopatterning applications without manipulation of the surface chemistry or the application of external fields.

Selective Metallization of Well Aligned PS-b-P2VP Block Copolymers in Thin Films and in Confined Geometries

NASA Astrophysics Data System (ADS)

Sievert, James D.; Watkins, James J.; Russell, Thomas P.

2006-03-01

Well aligned, microphase-separated structures of styrene-2-vinylpyridine block copolymers are being used as templates for macromolecule-metal nanocomposites. These composites are either prepared as thin films or confined in nanoporous aluminum oxide membranes. Under optimal conditions, templates are prepared as thin films or confined nanorods and metallized without disturbing the ordered structure. We have developed a procedure that deposits metal within the polymer using supercritical carbon dioxide-soluble metal precursors. The use of supercritical carbon dioxide allows for selective metallization of the polymer at or below the glass transition, without disrupting the morphology. In addition, similar procedures have been investigated using metal salts and acids. Using these techniques, metals and metal-sulfides including silver, gold, platinum and zinc sulfide have been selectively deposited.

Functionalized nanoporous silicas for the immobilization of penicillin acylase

NASA Astrophysics Data System (ADS)

Maria Chong, A. S.; Zhao, X. S.

2004-10-01

Nanoporous silica materials with uniform pore size and ordered structure have drawn growing interest of researchers since 1990s. A large-pore nanoporous material, SBA-15, was functionalized with organosilanes by co-condensation method in the presence of nonionic triblock copolymer P123 as a template under acidic conditions. The functionalization was demonstrated by using five organosilanes, namely 3-aminopropyltriethoxysilane (APTES), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltriethoxysilane (VTES), and 4-(triethoxysilyl)butyronitrile (TSBN), which modified the surface properties of the silica materials, enabling the materials to be a promising support for immobilization of biological molecules. The functionalized SBA-15 materials exhibited long-range ordering of two-dimensional hexagonal pore arrays of size ranging from 66 to 90 Å as demonstrated by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and physical adsorption techniques. A variety of organosilane density in the range of 0.5-2.6 mmol/g was achieved as revealed by elemental analysis and solid-state nuclear magnetic resonance (NMR) techniques. The functionalized materials displayed improved properties for immobilization of penicillin acylase (PA) in comparison with pure-silica SBA-15. Such improvement is believed to be due to the enhanced surface hydrophobicity and electrostatic interactions of the functional groups with the enzyme.

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

PubMed Central

Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

2015-01-01

The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

Asymmetric organic-inorganic hybrid membrane formation via block copolymer-nanoparticle co-assembly.

PubMed

Gu, Yibei; Dorin, Rachel M; Wiesner, Ulrich

2013-01-01

A facile method for forming asymmetric organic-inorganic hybrid membranes for selective separation applications is developed. This approach combines co-assembly of block copolymer (BCP) and inorganic nanoparticles (NPs) with non-solvent induced phase separation. The method is successfully applied to two distinct molar mass BCPs with different fractions of titanium dioxide (TiO2) NPs. The resulting hybrid membranes exhibit structural asymmetry with a thin nanoporous surface layer on top of a macroporous fingerlike support layer. Key parameters that dictate membrane surface morphology include the fraction of inorganics used and the length of time allowed for surface layer development. The resulting membranes exhibit both good selectivity and high permeability (3200 ± 500 Lm(-2) h(-1) bar(-1)). This fast and straightforward synthesis method for asymmetric hybrid membranes provides a new self-assembly platform upon which multifunctional and high-performance organic-inorganic hybrid membranes can be formed.

Applications of Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Meth, Jeffrey

Polymer nanocomposites have been developed for application in several areas. This talk will provide three vignettes of applications that have been explored. Nanoporous ceramics are free standing ceramic objects that can be used for filtration. The pore size distribution is in the proper target range for filtering viruses from medicines in solution. Filled polyimides are useful for improving the ultimate electrical properties of insulating films during corona exposure. The advantages and pitfalls of this approach will be detailed. Exfoliated laponite dispersed into ethylene copolymers reduces creep while maintaining transparency, which is applicable to packaging.

General method for the synthesis of hierarchical nanocrystal-based mesoporous materials.

PubMed

Rauda, Iris E; Buonsanti, Raffaella; Saldarriaga-Lopez, Laura C; Benjauthrit, Kanokraj; Schelhas, Laura T; Stefik, Morgan; Augustyn, Veronica; Ko, Jesse; Dunn, Bruce; Wiesner, Ulrich; Milliron, Delia J; Tolbert, Sarah H

2012-07-24

Block copolymer templating of inorganic materials is a robust method for the production of nanoporous materials. The method is limited, however, by the fact that the molecular inorganic precursors commonly used generally form amorphous porous materials that often cannot be crystallized with retention of porosity. To overcome this issue, here we present a general method for the production of templated mesoporous materials from preformed nanocrystal building blocks. The work takes advantage of recent synthetic advances that allow organic ligands to be stripped off of the surface of nanocrystals to produce soluble, charge-stabilized colloids. Nanocrystals then undergo evaporation-induced co-assembly with amphiphilic diblock copolymers to form a nanostructured inorganic/organic composite. Thermal degradation of the polymer template results in nanocrystal-based mesoporous materials. Here, we show that this method can be applied to nanocrystals with a broad range of compositions and sizes, and that assembly of nanocrystals can be carried out using a broad family of polymer templates. The resultant materials show disordered but homogeneous mesoporosity that can be tuned through the choice of template. The materials also show significant microporosity, formed by the agglomerated nanocrystals, and this porosity can be tuned by the nanocrystal size. We demonstrate through careful selection of the synthetic components that specifically designed nanostructured materials can be constructed. Because of the combination of open and interconnected porosity, high surface area, and compositional tunability, these materials are likely to find uses in a broad range of applications. For example, enhanced charge storage kinetics in nanoporous Mn(3)O(4) is demonstrated here.

The Earth’s Radiation Belts.

DTIC Science & Technology

1983-09-20

on -- 1d. It --- . d id-er, c S, blck -.o~b.1) ’Trapped radiation Steady-state miodels Adiabatic invariants Empirical flux models Diffusion equations...Shell -splitting, Transport theory Nuclear detonations Wave-oarticle interactions Effects on microelectronics 20 ABSTRACT ( C -0- n OR e -~ d . It -~e-lay...olo -i t i os5 at 500 ke\\% live lrtI’m i s pt, eOI iS .1: litv, ,Ie It if 5)ht* stIweo f iul-’t, wi te thle hie av itk, i il - il v t’il 1 Ltt sI c a

A Methodology for Producing and Testing a Genesil Silicon Compiler Designed VLSI Chip Which Incorporates Design for Testability

DTIC Science & Technology

1990-09-01

Monterey, California 93943-5000 Monterey, California 93943-5000 8a NAME OF OjNYNG SPONSORNc Br Oc.(C S VBO_ 9 POCAE’ ,S’ jN1N DE NT CA (’% . ORGANIZATON (If...position of the Depart- ment of Defense or the US Government. ś COSA I CODL> 18 S,,BjECT TERMS (Continue on reverse if necessar dno idenritj b blck...logic for which it was de - signed. Finally, the circuit should retain correct function- ality over time by having stable operating characteristics. If

Block Copolymer-Templated Approach to Nanopatterned Metal-Organic Framework Films.

PubMed

Zhou, Meimei; Wu, Yi-Nan; Wu, Baozhen; Yin, Xianpeng; Gao, Ning; Li, Fengting; Li, Guangtao

2017-08-17

The fabrication of patterned metal-organic framework (MOF) films with precisely controlled nanoscale resolution has been a fundamental challenge in nanoscience and nanotechnology. In this study, nanopatterned MOF films were fabricated using a layer-by-layer (LBL) growth method on functional templates (such as a bicontinuous nanoporous membrane or a structure with highly long-range-ordered nanoscopic channels parallel to the underlying substrate) generated by the microphase separation of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) block copolymers. HKUST-1 can be directly deposited on the templates without any chemical modification because the pyridine groups in P2VP interact with metal ions via metal-BCP complexes. As a result, nanopatterned HKUST-1 films with feature sizes below 50 nm and controllable thicknesses can be fabricated by controlling the number of LBL growth cycles. The proposed fabrication method further extends the applications of MOFs in various fields. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase behavior of model ABC triblock copolymers

NASA Astrophysics Data System (ADS)

Chatterjee, Joon

The phase behavior of poly(isoprene-b-styrene- b-ethylene oxide) (ISO), a model ABC triblock copolymer has been studied. This class of materials exhibit self-assembly, forming a large array of ordered morphologies at length scales of 5-100 nm. The formation of stable three-dimensionally continuous network morphologies is of special interest in this study. Since these nanostructures considerably impact the material properties, fundamental knowledge for designing ABC systems have high technological importance for realizing applications in the areas of nanofabrication, nanoporous media, separation membranes, drug delivery and high surface area catalysts. A comprehensive framework was developed to describe the phase behavior of the ISO triblock copolymers at weak to intermediate segregation strengths spanning a wide range of composition. Phases were characterized through a combination of characterization techniques, including small angle x-ray scattering, dynamic mechanical spectroscopy, transmission electron microscopy, and birefringence measurements. Combined with previous investigations on ISO, six different stable ordered state symmetries have been identified: lamellae (LAM), Fddd orthorhombic network (O70), double gyroid (Q230), alternating gyroid (Q214), hexagonal (HEX), and body-centered cubic (BCC). The phase map was found to be somewhat asymmetric around the fI = fO isopleth. This work provides a guide for theoretical studies and gives insight into the intricate effects of various parameters on the self-assembly of ABC triblock copolymers. Experimental SAXS data evaluated with a simple scattering intensity model show that local mixing varies continuously across the phase map between states of two- and three-domain segregation. Strategies of blending homopolymers with ISO triblock copolymer were employed for studying the swelling properties of a lamellar state. Results demonstrate that lamellar domains swell or shrink depending upon the type of homopolymer that was mixed. The results provide insight into the chain conformation of ABC triblock copolymers, where the B blocks are completely bridged across the adjacent A and C domains. In the final part of the thesis, the swelling properties were used to study the directed assembly of ABC triblock copolymers on chemically nanopatterned surfaces.

Control of both particle and pore size in nanoporous palladium alloy powders

DOE PAGES

Jones, Christopher G.; Cappillino, Patrick J.; Stavila, Vitalie; ...

2014-07-15

Energy storage materials often involve chemical reactions with bulk solids. Porosity within the solids can enhance reaction rates. The porosity can be either within or between individual particles of the material. Greater control of the size and uniformity of both types of pore should lead to enhancements of charging and discharging rates in energy storage systems. Furthermore, to control both particle and pore size in nanoporous palladium (Pd)-based hydrogen storage materials, first we created uniformly sized copper particles of about 1 μm diameter by the reduction of copper sulfate with ascorbic acid. In turn, these were used as reducing agentsmore » for tetrachloropalladate in the presence of a block copolymer surfactant. The copper reductant particles are geometrically self-limiting, so the resulting Pd particles are of similar size. The surfactant induces formation of 10 nm-scale pores within the particles. Some residual copper is alloyed with the Pd, reducing hydrogen storage capacity; use of a more reactive Pd salt can mitigate this. The reaction is conveniently performed in gram-scale batches.« less

Blueprint for Change. Report of the Process Action Team on Military Specifications and Standards

DTIC Science & Technology

1994-03-01

and Standards 6. AlfT"OR( S ) DoD Process Action Team N/A 7. PRFORP-INQ ORGAN-AT!,N NA t( S ) ANO II PERFORAM NG ORGANI/AHIUN HQ, U.S. Army Materiel Command...AGENCY NANI,: , S ) AND ADIPESSES) 10. SPONSORiNG, MONITORING Deputy Under Secretary of Defense for Acquisition Reform AGEN4CY REPORT NUMBER Ms. Colleen...special markings in all capitals (e.g. Jan SB). u’t coe at Ioo’J tht- yearj NC)FORN, REL, ITAR). Blck3.1 V1, -)" -Z". f It- Ir r -D It S Cov T --,D OD

Magnetic field alignment of coil-coil diblock copolymers and blends via intrinsic chain anisotropy

NASA Astrophysics Data System (ADS)

Rokhlenko, Yekaterina; Majewski, Pawel; Larson, Steven; Yager, Kevin; Gopalan, Padma; Avgeropoulos, Apostolos; Chan, Edwin; Osuji, Chinedum

Magnetic fields can control alignment of self-assembled soft materials such as block copolymers provided there is a suitably large magnetic susceptibility anisotropy present in the system. Recent results have highlighted the existence of a non-trivial intrinsic anisotropy in coil-coil diblock copolymers, specifically in lamellar-forming PS-b-P4VP, which enables alignment at field strengths of a few tesla in systems lacking mesogenic components. Alignment is predicated on correlation in the orientation of end-end vectors implied by the localization of block junctions at the microdomain interface and is observed on cooling across the order-disorder transition in the presence of the field. For appropriate combinations of field strength and grain size, we can leverage intrinsic chain anisotropy to magnetically direct self-assembly of many non-mesogenic systems, including other coil-coil BCPs like PS-b-PDMS and PS-b-PMMA, blends of BCPs of disparate morphologies and MWs, and blends of BCPs with homopolymers. This is noteworthy as blends of PS-b-P4VP with PEO provide a route to form functional materials such as nanoporous films by dissolution of PEO, or aligned ion conduction materials. We survey these various systems using TEM and in-situ X-ray scattering to study the phase behavior and temperature-, time- and field- dependent dynamics of alignment.

Immobilization of glucose oxidase to nanostructured films of polystyrene-block-poly(2-vinylpyridine).

PubMed

Bhakta, Samir A; Benavidez, Tomas E; Garcia, Carlos D

2014-09-15

A critical step for the development of biosensors is the immobilization of the biorecognition element to the surface of a substrate. Among other materials that can be used as substrates, block copolymers have the untapped potential to provide significant advantages for the immobilization of proteins. To explore such possibility, this manuscript describes the fabrication and characterization of thin-films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP). These films were then used to investigate the immobilization of glucose oxidase, a model enzyme for the development of biosensors. According to the results presented, the nanoporous films can provide significant increases in surface area of the substrate and the immobilization of larger amounts of active enzyme. The characterization of the substrate-enzyme interface discussed in the manuscript aims to provide critical information about relationship between the surface (material, geometry, and density of pores), the protein structure, and the immobilization conditions (pH, and protein concentration) required to improve the catalytic activity and stability of the enzymes. A maximum normalized activity of 3300±700 U m(-2) was achieved for the nanoporous film of PS-b-P2VP. Copyright © 2014 Elsevier Inc. All rights reserved.

Immobilization of Glucose Oxidase to Nanostructured Films of Polystyrene-block-poly(2-vinylpyridine)

PubMed Central

Bhakta, Samir A; Benavidez, Tomas E; Garcia, Carlos D

2014-01-01

A critical step for the development of biosensors is the immobilization of the biorecognition element to the surface of a substrate. Among other materials that can be used as substrates, block copolymers have the untapped potential to provide significant advantages for the immobilization of proteins. To explore such possibility, this manuscript describes the fabrication and characterization of thin-films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP). These films were then used to investigate the immobilization of glucose oxidase, a model enzyme for the development of biosensors. According to the results presented, the nanoporous films can provide significant increases in surface area of the substrate and the immobilization of larger amounts of active enzyme. The characterization of the substrate-enzyme interface discussed in the manuscript aims to provide critical information about relationship between the surface (material, geometry, and density of pores), the protein structure, and the immobilization conditions (pH, ionic strength, and protein concentration) required to improve the catalytic activity and stability of the enzymes. A maximum normalized activity of 3300 ± 700 U m−2 was achieved for the nanoporous film of PS-b-P2VP. PMID:24980481

Structural Transformation of Diblock Copolymer/Homopolymer Assemblies by Tuning Cylindrical Confinement and Interfacial Interactions.

PubMed

Xu, Jiangping; Wang, Ke; Liang, Ruijing; Yang, Yi; Zhou, Huamin; Xie, Xiaolin; Zhu, Jintao

2015-11-17

In this study, we report the controllable structural transformation of block copolymer/homopolymer binary blends in cylindrical nanopores. Polystyrene-b-poly(4-vinylpyridine)/homopolystyrene (SVP/hPS) nanorods (NRs) can be fabricated by pouring the polymers into an anodic aluminum oxide (AAO) channel and isolated by selective removal of the AAO membrane. In this two-dimensional (2D) confinement, SVP self-assembles into NRs with concentric lamellar structure, and the internal structure can be tailored with the addition of hPS. We show that the weight fraction and molecular weight of hPS and the diameter of the channels can significantly affect the internal structure of the NRs. Moreover, mesoporous materials with tunable pore shape, size, and packing style can be prepared by selective solvent swelling of the structured NRs. In addition, these NRs can transform into spherical structures through solvent-absorption annealing, triggering the conversion from 2D to 3D confinement. More importantly, the transformation dynamics can be tuned by varying the preference property of surfactant to the polymers. It is proven that the shape and internal structure of the polymer particles are dominated by the interfacial interactions governed by the surfactants.

An emerging pore-making strategy: confined swelling-induced pore generation in block copolymer materials.

PubMed

Wang, Yong; Li, Fengbin

2011-05-17

Block copolymers (BCPs) composed of two or more thermodynamically incompatible homopolymers self-assemble into periodic microdomains. Exposing self-assembled BCPs with solvents selective to one block causes a swelling of the domains composed of this block. Strong swelling in the confinement imposed by the matrix of the other glassy block leads to well-defined porous structures via morphology reconstruction. This confined swelling-induced pore-making process has emerged recently as a new strategy to produce porous materials due to synergic advantages that include extreme simplicity, high pore regularity, involvement of no chemical reactions, no weight loss, reversibility of the pore forming process, etc. The mechanism, kinetics, morphology, and governing parameters of the confined swelling-induced pore-making process in BCP thin films are discussed, and the main applications of nanoporous thin films in the fields of template synthesis, surface patterning, and guidance for the areal arrangements of nanomaterials and biomolecules are summarized. Recent, promising results of extending this mechanism to produce BCP nanofibers or nanotubes and bulk materials with well-defined porosity, which makes this strategy also attractive to researchers outside the nanocommunity, are also presented. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Orientational control of block copolymer microdomains by sub-tesla magnetic fields

NASA Astrophysics Data System (ADS)

Gopinadhan, Manesh; Choo, Youngwoo; Feng, Xunda; Kawabata, Kohsuke; di, Xiaojun; Osuji, Chinedum

Magnetic fields offer a versatile approach to controlling the orientation of block copolymer (BCP) microdomains during self-assembly. To date however, such control has required the imposition of large magnetic fields (>3T), necessitating the use of complex magnet systems - either superconducting or very large conventional resistive magnets. Here we demonstrate the ability to direct BCP self-assembly using considerably smaller fields (<1T) which are accessible using simple rare-earth permanent magnets. The low field alignment is enabled by the presence of small quantities of mesogenic species that are blended into, and co-assemble with the liquid crystalline (LC) mesophase of the side-chain LC BCP under study. In situ SAXS experiments reveal a pronounced dependence of the critical alignment field strength on the stoichiometry of the blend, and the ability to generate aligned microdomains with orientational distribution coefficients exceeding 0.95 at sub-1 T fields for appropriate stoichiometries. The alignment response overall can be rationalized in terms of increased mobility and grain size due to the presence of the mesogenic additive. We use a permanent magnet to fabricate films with aligned nanopores, and the utility of this approach to generate complex BCP microdomain patterns in thin films by local field screening are highlighted. NSF DMR-1410568 and DMR-0847534.

A temperature, pH and sugar triple-stimuli-responsive nanofluidic diode.

PubMed

Zheng, Yu-Bin; Zhao, Shuang; Cao, Shuo-Hui; Cai, Sheng-Lin; Cai, Xiu-Hong; Li, Yao-Qun

2017-01-07

In this article, we have demonstrated for the first time a triple stimuli-responsive nanofluidic diode that can rectify ionic current under multiple external stimuli including temperature, pH, and sugar. This diode was fabricated by immobilizing poly[2-(dimethylamino)ethyl methacrylate]-co-[4-vinyl phenylboronic acid] (P(DMAEMA-co-VPBA)) onto the wall of a single glass conical nanopore channel via surface-initiator atom transfer radical polymerization (SI-ATRP). The copolymer brushes contain functional groups sensitive to pH, temperature and sugar that can induce charge and configuration change to affect the status of the pore wall. The experimental results confirmed that the P(DMAEMA-co-VPBA) brush modified nanochannel regulated the ionic current rectification successfully under three different external stimuli. This biomimetically inspired research simulates the complex biological multi-functions of ion channels and promotes the development of "smart" biomimetic nanochannel systems for actuating and sensing applications.

Superhydrophobic nanofluidic channels for enhanced electrokinetic conversion

NASA Astrophysics Data System (ADS)

Checco, Antonio; Al Hossain, Aktaruzzaman; Rahmani, Amir; Black, Charles; Doerk, Gregory; Colosqui, Carlos

2017-11-01

We present current efforts in the development of novel slit nanofluidic channels with superhydrophobic nanostructured surfaces designed to enhance hydrodynamic conductivity and improve selective transport and electrokinetic energy conversion efficiencies (mechanical-electrical energy conversion). The nanochannels are fabricated on silicon wafers using UV lithography, and their internal surface is patterned with conical nanostructures (feature size and spacing 30 nm) defined by block copolymer self-assembly and plasma etching. These nanostructures are rendered superhydrophobic by passivation with a hydrophobic silane monolayer. We experimentally characterize hydrodynamic conductivity, effective zeta potentials, and eletrokinetic flows for the patterned nanochannels, comparing against control channels with bare surfaces. Experimental observations are rationalized using both continuum-based modeling and molecular dynamics simulations. Scientific and technical knowledge produced by this work is particularly relevant for sustainable energy conversion and storage, separation processes and water treatment using nanoporous materials. The ONR Contract # N000141613178 and NSF-CBET award# 1605809.

Expanding the functionality and applications of nanopore sensors

NASA Astrophysics Data System (ADS)

Venta, Kimberly E.

Nanopore sensors have developed into powerful tools for single-molecule studies since their inception two decades ago. Nanopore sensors function as nanoscale Coulter counters, by monitoring ionic current modulations as particles pass through a nanopore. While nanopore sensors can be used to study any nanoscale particle, their most notable application is as a low cost, fast alternative to current DNA sequencing technologies. In recent years, signifcant progress has been made toward the goal of nanopore-based DNA sequencing, which requires an ambitious combination of a low-noise and high-bandwidth nanopore measurement system and spatial resolution. In this dissertation, nanopore sensors in thin membranes are developed to improve dimensional resolution, and these membranes are used in parallel with a high-bandwidth amplfier. Using this nanopore sensor system, the signals of three DNA homopolymers are differentiated for the first time in solid-state nanopores. The nanopore noise is also reduced through the addition of a layer of SU8, a spin-on polymer, to the supporting chip structure. By increasing the temporal and spatial resolution of nanopore sensors, studies of shorter molecules are now possible. Nanopore sensors are beginning to be used for the study and characterization of nanoparticles. Nanoparticles have found many uses from biomedical imaging to next-generation solar cells. However, further insights into the formation and characterization of nanoparticles would aid in developing improved synthesis methods leading to more effective and customizable nanoparticles. This dissertation presents two methods of employing nanopore sensors to benet nanoparticle characterization and fabrication. Nanopores were used to study the formation of individual nanoparticles and serve as nanoparticle growth templates that could be exploited to create custom nanoparticle arrays. Additionally, nanopore sensors were used to characterize the surface charge density of anisotropic nanopores, which previously could not be reliably measured. Current nanopore sensor resolution levels have facilitated innovative research on nanoscale systems, including studies of DNA and nanoparticle characterization. Further nanopore system improvements will enable vastly improved DNA sequencing capabilities and open the door to additional nanopore sensing applications.

Influence of Nanopore Shapes on Thermal Conductivity of Two-Dimensional Nanoporous Material.

PubMed

Huang, Cong-Liang; Huang, Zun; Lin, Zi-Zhen; Feng, Yan-Hui; Zhang, Xin-Xin; Wang, Ge

2016-12-01

The influence of nanopore shapes on the electronic thermal conductivity (ETC) was studied in this paper. It turns out that with same porosity, the ETC will be quite different for different nanopore shapes, caused by the different channel width for different nanopore shapes. With same channel width, the influence of different nanopore shapes can be approximately omitted if the nanopore is small enough (smaller than 0.5 times EMFP in this paper). The ETC anisotropy was discovered for triangle nanopores at a large porosity with a large nanopore size, while there is a similar ETC for small pore size. It confirmed that the structure difference for small pore size may not be seen by electrons in their moving.

Microfluidic multiplexing of solid-state nanopores

NASA Astrophysics Data System (ADS)

Jain, Tarun; Rasera, Benjamin C.; Guerrero, Ricardo Jose S.; Lim, Jong-Min; Karnik, Rohit

2017-12-01

Although solid-state nanopores enable electronic analysis of many clinically and biologically relevant molecular structures, there are few existing device architectures that enable high-throughput measurement of solid-state nanopores. Herein, we report a method for microfluidic integration of multiple solid-state nanopores at a high density of one nanopore per (35 µm2). By configuring microfluidic devices with microfluidic valves, the nanopores can be rinsed from a single fluid input while retaining compatibility for multichannel electrical measurements. The microfluidic valves serve the dual purpose of fluidic switching and electric switching, enabling serial multiplexing of the eight nanopores with a single pair of electrodes. Furthermore, the device architecture exhibits low noise and is compatible with electroporation-based in situ nanopore fabrication, providing a scalable platform for automated electronic measurement of a large number of integrated solid-state nanopores.

Threading DNA through nanopores for biosensing applications

NASA Astrophysics Data System (ADS)

Fyta, Maria

2015-07-01

This review outlines the recent achievements in the field of nanopore research. Nanopores are typically used in single-molecule experiments and are believed to have a high potential to realize an ultra-fast and very cheap genome sequencer. Here, the various types of nanopore materials, ranging from biological to 2D nanopores are discussed together with their advantages and disadvantages. These nanopores can utilize different protocols to read out the DNA nucleobases. Although, the first nanopore devices have reached the market, many still have issues which do not allow a full realization of a nanopore sequencer able to sequence the human genome in about a day. Ways to control the DNA, its dynamics and speed as the biomolecule translocates the nanopore in order to increase the signal-to-noise ratio in the reading-out process are examined in this review. Finally, the advantages, as well as the drawbacks in distinguishing the DNA nucleotides, i.e., the genetic information, are presented in view of their importance in the field of nanopore sequencing.

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

PubMed

Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2013-12-13

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained. Copyright © 2013. Published by Elsevier B.V.

PS-b-PMMA/PLA blends for nanoporous templates with hierarchical and tunable pore size

NASA Astrophysics Data System (ADS)

Nguyen, Thi-Hoa; Vayer, Marylène; Sinturel, Christophe

2018-01-01

Blends of poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) and poly(lactide) (PLA) were deposited in the form of thin films on the surface of modified silicon wafers and exposed to tetrahydrofuran (THF) vapor annealing. It was shown that in specific experimental conditions, a core-shell morphology consisting in cylinders with a PMMA shell and a PLA core, within a continuous matrix of PS, was formed. In this case, PLA naturally segregated in the core of the PMMA cylinders, minimizing the PS/PLA interaction, which constitutes the most incompatible pair (the interaction strength between the various components was confirmed in thin films of the corresponding polymer blends). Compared to other block copolymer/homopolymer blends described in the literature, this system exhibits unexpected high increase of the characteristic lengths of the system (center-to-center distance and diameter). This was attributed to a partial solubilization of the PLA in the PMMA corona (the two polymers are highly compatible), inducing an enhanced level of PS and PLA stretching caused by the strong repulsion between these two polymers. The selective extraction of the PLA yielded to porous domains with small dimensions (6 ± 2.5 nm), reaching the performances that are currently attained in highly incompatible block polymers with low molecular weight. Further PMMA removal revealed a second porosity level, with higher pores diameter and center-to-center distance compared to the neat PS-b-PMMA system. This work highlights how PS-b-PMMA, that currently represents one of the industrial standards nanoporous template precursors, can be modified in an easy and costless approach using PLA homopolymer addition.

Single-molecule nanopore enzymology

PubMed Central

Wloka, Carsten; Maglia, Giovanni

2017-01-01

Biological nanopores are a class of membrane proteins that open nanoscale water-conduits in biological membranes. When they are reconstituted in artificial membranes and a bias voltage is applied across the membrane, the ionic current passing through individual nanopores can be used to monitor chemical reactions, to recognize individual molecules and, of most interest, to sequence DNA. More recently, proteins and enzymes have started being analysed with nanopores. Monitoring enzymatic reactions with nanopores, i.e. nanopore enzymology, has the unique advantage that it allows long-timescale observations of native proteins at the single-molecule level. Here we describe the approaches and challenges in nanopore enzymology. PMID:28630164

Nanopore thin film enabled optical platform for drug loading and release.

PubMed

Song, Chao; Che, Xiangchen; Que, Long

2017-08-07

In this paper, a drug loading and release device fabricated using nanopore thin film and layer-by-layer (LbL) nanoassembly is reported. The nanopore thin film is a layer of anodic aluminum oxide (AAO), consisting of honeycomb-shape nanopores. Using the LbL nanoassembly process, the drug, using gentamicin sulfate (GS) as the model, can be loaded into the nanopores and the stacked layers on the nanopore thin film surface. The drug release from the device is achieved by immersing it into flowing DI water. Both the loading and release processes can be monitored optically. The effect of the nanopore size/volume on drug loading and release has also been evaluated. Further, the neuron cells have been cultured and can grow normally on the nanopore thin film, verifying its bio-compatibility. The successful fabrication of nanopore thin film device on silicon membrane render it as a potential implantable controlled drug release device.

Ion transport in a pH-regulated nanopore.

PubMed

Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2013-08-06

Fundamental understanding of ion transport phenomena in nanopores is crucial for designing the next-generation nanofluidic devices. Due to surface reactions of dissociable functional groups on the nanopore wall, the surface charge density highly depends upon the proton concentration on the nanopore wall, which in turn affects the electrokinetic transport of ions, fluid, and particles within the nanopore. Electrokinetic ion transport in a pH-regulated nanopore, taking into account both multiple ionic species and charge regulation on the nanopore wall, is theoretically investigated for the first time. The model is verified by the experimental data of nanopore conductance available in the literature. The results demonstrate that the spatial distribution of the surface charge density at the nanopore wall and the resulting ion transport phenomena, such as ion concentration polarization (ICP), ion selectivity, and conductance, are significantly affected by the background solution properties, such as the pH and salt concentration.

Single Molecule Sensing by Nanopores and Nanopore Devices

PubMed Central

Gu, Li-Qun; Shim, Ji Wook

2010-01-01

Molecular-scale pore structures, called nanopores, can be assembled by protein ion channels through genetic engineering or be artificially fabricated on solid substrates using fashion nanotechnology. When target molecules interact with the functionalized lumen of a nanopore, they characteristically block the ion pathway. The resulting conductance changes allow for identification of single molecules and quantification of target species in the mixture. In this review, we first overview nanopore-based sensory techniques that have been created for the detection of myriad biomedical targets, from metal ions, drug compounds, and cellular second messengers to proteins and DNA. Then we introduce our recent discoveries in nanopore single molecule detection: (1) using the protein nanopore to study folding/unfolding of the G-quadruplex aptamer; (2) creating a portable and durable biochip that is integrated with a single-protein pore sensor (this chip is compared with recently developed protein pore sensors based on stabilized bilayers on glass nanopore membranes and droplet interface bilayer); and (3) creating a glass nanopore-terminated probe for single-molecule DNA detection, chiral enantiomer discrimination, and identification of the bioterrorist agent ricin with an aptamer-encoded nanopore. PMID:20174694

Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions

PubMed Central

2018-01-01

Pore-based structures occur widely in living organisms. Ion channels embedded in cell membranes, for example, provide pathways, where electron and proton transfer are coupled to the exchange of vital molecules. Learning from mother nature, a recent surge in activity has focused on artificial nanopore architectures to effect electrochemical transformations not accessible in larger structures. Here, we highlight these exciting advances. Starting with a brief overview of nanopore electrodes, including the early history and development of nanopore sensing based on nanopore-confined electrochemistry, we address the core concepts and special characteristics of nanopores in electron transfer. We describe nanopore-based electrochemical sensing and processing, discuss performance limits and challenges, and conclude with an outlook for next-generation nanopore electrode sensing platforms and the opportunities they present. PMID:29392173

Integrating Sub-3 nm Plasmonic Gaps into Solid-State Nanopores.

PubMed

Shi, Xin; Verschueren, Daniel; Pud, Sergii; Dekker, Cees

2018-05-01

Plasmonic nanopores combine the advantages of nanopore sensing and surface plasmon resonances by introducing confined electromagnetic fields to a solid-state nanopore. Ultrasmall nanogaps between metallic nanoantennas can generate the extremely enhanced localized electromagnetic fields necessary for single-molecule optical sensing and manipulation. Challenges in fabrication, however, hamper the integration of such nanogaps into nanopores. Here, a top-down approach for integrating a plasmonic antenna with an ultrasmall nanogap into a solid-state nanopore is reported. Employing a two-step e-beam lithography process, the reproducible fabrication of nanogaps down to a sub-1 nm scale is demonstrated. Subsequently, nanopores are drilled through the 20 nm SiN membrane at the center of the nanogap using focused-electron-beam sculpting with a transmission electron microscope, at the expense of a slight gap expansion for the smallest gaps. Using this approach, sub-3 nm nanogaps can be readily fabricated on solid-state nanopores. The functionality of these plasmonic nanopores for single-molecule detection is shown by performing DNA translocations. These integrated devices can generate intense electromagnetic fields at the entrance of the nanopore and can be expected to find applications in nanopore-based single-molecule trapping and optical sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanopore fabricated in pyramidal HfO2 film by dielectric breakdown method

NASA Astrophysics Data System (ADS)

Wang, Yifan; Chen, Qi; Deng, Tao; Liu, Zewen

2017-10-01

The dielectric breakdown method provides an innovative solution to fabricate solid-state nanopores on insulating films. A nanopore generation event via this method is considered to be caused by random charged traps (i.e., structural defects) and high electric fields in the membrane. Thus, the position and number of nanopores on planar films prepared by the dielectric breakdown method is hard to control. In this paper, we propose to fabricate nanopores on pyramidal HfO2 films (10-nm and 15-nm-thick) to improve the ability to control the location and number during the fabrication process. Since the electric field intensity gets enhanced at the corners of the pyramid-shaped film, the probability of nanopore occurrence at vertex and edge areas increases. This priority of appearance provides us chance to control the location and number of nanopores by monitoring a sudden irreversible discrete increase in current. The experimental results showed that the probability of nanopore occurrence decreases in an order from the vertex area, the edge area to the side face area. The sizes of nanopores ranging from 30 nm to 10 nm were obtained. Nanopores fabricated on the pyramid-shaped HfO2 film also showed an obvious ion current rectification characteristic, which might improve the nanopore performance as a biomolecule sequencing platform.

Discrimination of three types of homopolymers in single-stranded DNA with solid-state nanopores through external control of the DNA motion.

PubMed

Akahori, Rena; Yanagi, Itaru; Goto, Yusuke; Harada, Kunio; Yokoi, Takahide; Takeda, Ken-Ichi

2017-08-22

To achieve DNA sequencing with solid-state nanopores, the speed of the DNA in the nanopore must be controlled to obtain sequence-specific signals. In this study, we fabricated a nanopore-sensing system equipped with a DNA motion controller. DNA strands were immobilized on a Si probe, and approach of this probe to the nanopore vicinity could be controlled using a piezo actuator and stepper motor. The area of the Si probe was larger than the area of the membrane, which meant that the immobilized DNA could enter the nanopore without the need for the probe to scan to determine the location of the nanopore in the membrane. We demonstrated that a single-stranded DNA could be inserted into and removed from a nanopore in our experimental system. The number of different ionic-current levels observed while DNA remained in the nanopore corresponded to the number of different types of homopolymers in the DNA.

Large apparent electric size of solid-state nanopores due to spatially extended surface conduction.

PubMed

Lee, Choongyeop; Joly, Laurent; Siria, Alessandro; Biance, Anne-Laure; Fulcrand, Rémy; Bocquet, Lydéric

2012-08-08

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

Reaching the Ionic Current Detection Limit in Silicon-Based Nanopores

NASA Astrophysics Data System (ADS)

Puster, Matthew; Rodriguez-Manzo, Julio Alejandro; Nicolai, Adrien; Meunier, Vincent; Drndic, Marija

2015-03-01

Solid-state nanopores act as single-molecule sensors whereby passage of an individual molecule in aqueous electrolyte through a nanopore is registered as a change in ionic conductance (ΔG). Future nanopore applications such as DNA sequencing at high bandwidth require high ΔG for optimal signal-to-noise ratio. Reducing the nanopore diameter and thickness increase ΔG. Molecule size limits the diameter, thus efforts concentrate on minimizing the thickness by thinning oxide/nitride films or using 2D materials. Weighted by electrolyte conductivity the highest ΔG reported to date for DNA translocations were obtained with nanopores made in oxide/nitride films. We present a controlled electron irradiation technique to thin such films to the limit of their stability, producing nanopores tailored to molecule size in amorphous Si with thicknesses less than 2 nm. We compare ΔG values with results found in the literature for DNA translocation through these nanopores, where access resistance becomes comparable to the resistance through the nanopore itself.

Single cigar-shaped nanopores functionalized with amphoteric amino acid chains: experimental and theoretical characterization.

PubMed

Ali, Mubarak; Ramirez, Patricio; Nguyen, Hung Quoc; Nasir, Saima; Cervera, Javier; Mafe, Salvador; Ensinger, Wolfgang

2012-04-24

We present an experimental and theoretical characterization of single cigar-shaped nanopores with pH-responsive carboxylic acid and lysine chains functionalized on the pore surface. The nanopore characterization includes (i) optical images of the nanostructure obtained by FESEM; (ii) different chemical procedures for the nanopore preparation (etching time and functionalizations; pH and electrolyte concentration of the external solution) allowing externally tunable nanopore responses monitored by the current-voltage (I-V) curves; and (iii) transport simulations obtained with a multilayer nanopore model. We show that a single, approximately symmetric nanopore can be operated as a reconfigurable diode showing different rectifying behaviors by applying chemical and electrical signals. The remarkable characteristics of the new nanopore are the sharp response observed in the I-V curves, the improved tunability (with respect to previous designs of symmetric nanopores) which is achieved because of the direct external access to the nanostructure mouths, and the broad range of rectifying properties. The results concern both fundamental concepts useful for the understanding of transport processes in biological systems (ion channels) and applications relevant for tunable nanopore technology (information processing and drug controlled release).

Controlled formation of closed-edge nanopores in graphene

NASA Astrophysics Data System (ADS)

He, Kuang; Robertson, Alex W.; Gong, Chuncheng; Allen, Christopher S.; Xu, Qiang; Zandbergen, Henny; Grossman, Jeffrey C.; Kirkland, Angus I.; Warner, Jamie H.

2015-07-01

Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport.Dangling bonds at the edge of a nanopore in monolayer graphene make it susceptible to back-filling at low temperatures from atmospheric hydrocarbons, leading to potential instability for nanopore applications, such as DNA sequencing. We show that closed edge nanopores in bilayer graphene are robust to back-filling under atmospheric conditions for days. A controlled method for closed edge nanopore formation starting from monolayer graphene is reported using an in situ heating holder and electron beam irradiation within an aberration-corrected transmission electron microscopy. Tailoring of closed-edge nanopore sizes is demonstrated from 1.4-7.4 nm. These results should provide mechanisms for improving the stability of nanopores in graphene for a wide range of applications involving mass transport. Electronic supplementary information (ESI) available: Low magnification images, image processing techniques employed, modelling and simulation of closed edge nanoribbon, comprehensive AC-TEM dataset, and supporting analysis. See DOI: 10.1039/c5nr02277k

Stretching and Controlled Motion of Single-Stranded DNA in Locally-Heated Solid-State Nanopores

PubMed Central

Belkin, Maxim; Maffeo, Christopher; Wells, David B.

2013-01-01

Practical applications of solid-state nanopores for DNA detection and sequencing require the electrophoretic motion of DNA through the nanopores to be precisely controlled. Controlling the motion of single-stranded DNA presents a particular challenge, in part because of the multitude of conformations that a DNA strand can adopt in a nanopore. Through continuum, coarse-grained and atomistic modeling, we demonstrate that local heating of the nanopore volume can be used to alter the electrophoretic mobility and conformation of single-stranded DNA. In the nanopore systems considered, the temperature near the nanopore is modulated via a nanometer-size heater element that can be radiatively switched on and off. The local enhancement of temperature produces considerable stretching of the DNA fragment confined within the nanopore. Such stretching is reversible, so that the conformation of DNA can be toggled between compact (local heating is off) and extended (local heating is on) states. The effective thermophoretic force acting on single-stranded DNA in the vicinity of the nanopore is found to be sufficiently large (4–8 pN) to affect such changes in the DNA conformation. The local heating of the nanopore volume is observed to promote single-file translocation of DNA strands at transmembrane biases as low as 10 mV, which opens new avenues for using solid-state nanopores for detection and sequencing of DNA. PMID:23876013

Study on the Characteristics of Gas Molecular Mean Free Path in Nanopores by Molecular Dynamics Simulations

PubMed Central

Liu, Qixin; Cai, Zhiyong

2014-01-01

This paper presents studies on the characteristics of gas molecular mean free path in nanopores by molecular dynamics simulation. Our study results indicate that the mean free path of all molecules in nanopores depend on both the radius of the nanopore and the gas-solid interaction strength. Besides mean free path of all molecules in the nanopore, this paper highlights the gas molecular mean free path at different positions of the nanopore and the anisotropy of the gas molecular mean free path at nanopores. The molecular mean free path varies with the molecule’s distance from the center of the nanopore. The least value of the mean free path occurs at the wall surface of the nanopore. The present paper found that the gas molecular mean free path is anisotropic when gas is confined in nanopores. The radial gas molecular mean free path is much smaller than the mean free path including all molecular collisions occuring in three directions. Our study results also indicate that when gas is confined in nanopores the gas molecule number density does not affect the gas molecular mean free path in the same way as it does for the gas in unbounded space. These study results may bring new insights into understanding the gas flow’s characteristic at nanoscale. PMID:25046745

Atomic layer deposition of nanoporous biomaterials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narayan, R. J.; Adiga, S. P.; Pellin, M. J.

2010-03-01

Due to its chemical stability, uniform pore size, and high pore density, nanoporous alumina is being investigated for use in biosensing, drug delivery, hemodialysis, and other medical applications. In recent work, we have examined the use of atomic layer deposition for coating the surfaces of nanoporous alumina membranes. Zinc oxide coatings were deposited on nanoporous alumina membranes using atomic layer deposition. The zinc oxide-coated nanoporous alumina membranes demonstrated antimicrobial activity against Escherichia coli and Staphylococcus aureus bacteria. These results suggest that atomic layer deposition is an attractive technique for modifying the surfaces of nanoporous alumina membranes and other nanostructured biomaterials.more » Nanoporous alumina, also known as anodic aluminum oxide (AAO), is a nanomaterial that exhibits several unusual properties, including high pore densities, straight pores, small pore sizes, and uniform pore sizes. In 1953, Keller et al. showed that anodizing aluminum in acid electrolytes results in a thick layer of nearly cylindrical pores, which are arranged in a close-packed hexagonal cell structure. More recently, Matsuda & Fukuda demonstrated preparation of highly ordered platinum and gold nanohole arrays using a replication process. In this study, a negative structure of nanoporous alumina was initially fabricated and a positive structure of a nanoporous metal was subsequently fabricated. Over the past fifteen years, nanoporous alumina membranes have been used as templates for growth of a variety of nanostructured materials, including nanotubes, nanowires, nanorods, and nanoporous membranes.« less

Engineering the internal surfaces of three-dimensional nanoporous catalysts by surfactant-modified dealloying.

PubMed

Wang, Zhili; Liu, Pan; Han, Jiuhui; Cheng, Chun; Ning, Shoucong; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2017-10-20

Tuning surface structures by bottom-up synthesis has been demonstrated as an effective strategy to improve the catalytic performances of nanoparticle catalysts. Nevertheless, the surface modification of three-dimensional nanoporous metals, fabricated by a top-down dealloying approach, has not been achieved despite great efforts devoted to improving the catalytic performance of three-dimensional nanoporous catalysts. Here we report a surfactant-modified dealloying method to tailor the surface structure of nanoporous gold for amplified electrocatalysis toward methanol oxidation and oxygen reduction reactions. With the assistance of surfactants, {111} or {100} faceted internal surfaces of nanoporous gold can be realized in a controllable manner by optimizing dealloying conditions. The surface modified nanoporous gold exhibits significantly enhanced electrocatalytic activities in comparison with conventional nanoporous gold. This study paves the way to develop high-performance three-dimensional nanoporous catalysts with a tunable surface structure by top-down dealloying for efficient chemical and electrochemical reactions.

Ultra-Thin Solid-State Nanopores: Fabrication and Applications

NASA Astrophysics Data System (ADS)

Kuan, Aaron Tzeyang

Solid-state nanopores are a nanofluidic platform with unique advantages for single-molecule analysis and filtration applications. However, significant improvements in device performance and scalable fabrication methods are needed to make nanopore devices competitive with existing technologies. This dissertation investigates the potential advantages of ultra-thin nanopores in which the thickness of the membrane is significantly smaller than the nanopore diameter. Novel, scalable fabrication methods were first developed and then utilized to examine device performance for water filtration and single molecule sensing applications. Fabrication of nanometer-thin pores in silicon nitride membranes was achieved using a feedback-controlled ion beam method in which ion sputtering is arrested upon detection of the first few ions that drill through the membrane. Performing fabrication at liquid nitrogen temperatures prevents surface atom rearrangements that have previously complicated similar processes. A novel cross-sectional imaging method was also developed to allow careful examination of the full nanopore geometry. Atomically-thin graphene nanopores were fabricated via an electrical pulse method in which sub-microsecond electrical pulses applied across a graphene membrane in electrolyte solution are used to create a defect in the membrane and controllably enlarge it into a nanopore. This method dramatically increases the accuracy and reliability of graphene nanopore production, allowing consistent production of single nanopores down to subnanometer sizes. In filtration applications in which nanopores are used to selectively restrict the passage of dissolved contaminants, ultra-thin nanopores minimize the flow resistance, increasing throughput and energy-efficiency. The ability of graphene nanopores to separate different ions was characterized via ionic conductance and reversal potential measurements. Graphene nanopores were observed to conduct cations preferentially over anions with selectivity ratios of 100 or higher for pores as large as 20 nm in diameter, suggesting that porous graphene membranes can be used to create highly effective cation exchange membranes for electrodialysis filtration. These surprisingly high selectivities cannot be explained by current models of ionic conduction in graphene nanopores, motivating the development of a new model in which elevated concentrations of mobile cations near the graphene surface generate additional ion selectivity.

Recent Advances in Nanoporous Membranes for Water Purification

PubMed Central

Wang, Zhuqing; Colombi Ciacchi, Lucio

2018-01-01

Nanoporous materials exhibit wide applications in the fields of electrocatalysis, nanodevice fabrication, energy, and environmental science, as well as analytical science. In this review, we present a summary of recent studies on nanoporous membranes for water purification application. The types and fabrication strategies of various nanoporous membranes are first introduced, and then the fabricated nanoporous membranes for removing various water pollutants, such as salt, metallic ions, anions, nanoparticles, organic chemicals, and biological substrates, are demonstrated and discussed. This work will be valuable for readers to understand the design and fabrication of various nanoporous membranes, and their potential purification mechanisms towards different water pollutants. In addition, it will be helpful for developing new nanoporous materials for quick, economic, and high-performance water purification. PMID:29370128

A nanoporous gold membrane for sensing applications

PubMed Central

Oo, Swe Zin; Silva, Gloria; Carpignano, Francesca; Noual, Adnane; Pechstedt, Katrin; Mateos, Luis; Grant-Jacob, James A.; Brocklesby, Bill; Horak, Peter; Charlton, Martin; Boden, Stuart A.; Melvin, Tracy

2016-01-01

Design and fabrication of three-dimensionally structured, gold membranes containing hexagonally close-packed microcavities with nanopores in the base, are described. Our aim is to create a nanoporous structure with localized enhancement of the fluorescence or Raman scattering at, and in the nanopore when excited with light of approximately 600 nm, with a view to provide sensitive detection of biomolecules. A range of geometries of the nanopore integrated into hexagonally close-packed assemblies of gold micro-cavities was first evaluated theoretically. The optimal size and shape of the nanopore in a single microcavity were then considered to provide the highest localized plasmon enhancement (of fluorescence or Raman scattering) at the very center of the nanopore for a bioanalyte traversing through. The optimized design was established to be a 1200 nm diameter cavity of 600 nm depth with a 50 nm square nanopore with rounded corners in the base. A gold 3D-structured membrane containing these sized microcavities with the integrated nanopore was successfully fabricated and ‘proof of concept’ Raman scattering experiments are described. PMID:26973809

Effect of ultraviolet illumination and ambient gases on the photoluminescence and electrical properties of nanoporous silicon layer for organic vapor sensor.

PubMed

Atiwongsangthong, Narin

2012-08-01

The purpose of this research, the nanoporous silicon layer were fabricated and investigated the physical properties such as photoluminescence and the electrical properties in order to develop organic vapor sensor by using nanoporous silicon. The Changes in the photoluminescence intensity of nanoporous silicon samples are studied during ultraviolet illumination in various ambient gases such as nitrogen, oxigen and vacuum. In this paper, the nanoporous silicon layer was used as organic vapor adsorption and sensing element. The advantage of this device are simple process compatible in silicon technology and usable in room temperature. The structure of this device consists of nanoporous silicon layer which is formed by anodization of silicon wafer in hydrofluoric acid solution and aluminum electrode which deposited on the top of nanoporous silicon layer by evaporator. The nanoporous silicon sensors were placed in a gas chamber with various organic vapor such as ethanol, methanol and isopropyl alcohol. From studying on electrical characteristics of this device, it is found that the nanoporous silicon layer can detect the different organic vapor. Therefore, the nanoporous silicon is important material for organic vapor sensor and it can develop to other applications about gas sensors in the future.

Atomic layer deposition-based functionalization of materials for medical and environmental health applications

PubMed Central

Narayan, Roger J.; Adiga, Shashishekar P.; Pellin, Michael J.; Curtiss, Larry A.; Hryn, Alexander J.; Stafslien, Shane; Chisholm, Bret; Shih, Chun-Che; Shih, Chun-Ming; Lin, Shing-Jong; Su, Yea-Yang; Jin, Chunming; Zhang, Junping; Monteiro-Riviere, Nancy A.; Elam, Jeffrey W.

2010-01-01

Nanoporous alumina membranes exhibit high pore densities, well-controlled and uniform pore sizes, as well as straight pores. Owing to these unusual properties, nanoporous alumina membranes are currently being considered for use in implantable sensor membranes and water purification membranes. Atomic layer deposition is a thin-film growth process that may be used to modify the pore size in a nanoporous alumina membrane while retaining a narrow pore distribution. In addition, films deposited by means of atomic layer deposition may impart improved biological functionality to nanoporous alumina membranes. In this study, zinc oxide coatings and platinum coatings were deposited on nanoporous alumina membranes by means of atomic layer deposition. PEGylated nanoporous alumina membranes were prepared by self-assembly of 1-mercaptoundec-11-yl hexa(ethylene glycol) on platinum-coated nanoporous alumina membranes. The pores of the PEGylated nanoporous alumina membranes remained free of fouling after exposure to human platelet-rich plasma; protein adsorption, fibrin networks and platelet aggregation were not observed on the coated membrane surface. Zinc oxide-coated nanoporous alumina membranes demonstrated activity against two waterborne pathogens, Escherichia coli and Staphylococcus aureus. The results of this work indicate that nanoporous alumina membranes may be modified using atomic layer deposition for use in a variety of medical and environmental health applications. PMID:20308114

High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo

2015-09-16

Micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous Ni xCo (3-x)(CO 3) y and Ni xCo (3-x)O 4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline Ni xCo (3-x)O 4. The micelle templated mesopores are interconnected and providemore » transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g -1. Amongst the mixed-metal oxides, Ni 2CoO 4 exhibits the highest specific capacity of 239 mA h g -1 after galvanostatic cycling at a current density of 1 A g -1 for 10 cycles. We attribute the superior performance of Ni 2CoO 4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.« less

Multichannel detection of ionic currents through two nanopores fabricated on integrated Si3N4 membranes.

PubMed

Yanagi, Itaru; Akahori, Rena; Aoki, Mayu; Harada, Kunio; Takeda, Ken-Ichi

2016-08-16

Integration of solid-state nanopores and multichannel detection of signals from each nanopore are effective measures for realizing high-throughput nanopore sensors. In the present study, we demonstrated fabrication of Si3N4 membrane arrays and the simultaneous measurement of ionic currents through two nanopores formed in two adjacent membranes. Membranes with thicknesses as low as 6.4 nm and small nanopores with diameters of less than 2 nm could be fabricated using the poly-Si sacrificial-layer process and multilevel pulse-voltage injection. Using the fabricated nanopore membranes, we successfully achieved simultaneous detection of clear ionic-current blockades when single-stranded short homopolymers (poly(dA)60) passed through two nanopores. In addition, we investigated the signal crosstalk and leakage current among separated chambers. When two nanopores were isolated on the front surface of the membrane, there was no signal crosstalk or leakage current between the chambers. However, when two nanopores were isolated on the backside of the Si substrate, signal crosstalk and leakage current were observed owing to high-capacitance coupling between the chambers and electrolysis of water on the surface of the Si substrate. The signal crosstalk and leakage current could be suppressed by oxidizing the exposed Si surface in the membrane chip. Finally, the observed ionic-current blockade when poly(dA)60 passed through the nanopore in the oxidized chip was approximately half of that observed in the non-oxidized chip.

DNA translocation through graphene nanopores.

PubMed

Merchant, Christopher A; Healy, Ken; Wanunu, Meni; Ray, Vishva; Peterman, Neil; Bartel, John; Fischbein, Michael D; Venta, Kimberly; Luo, Zhengtang; Johnson, A T Charlie; Drndić, Marija

2010-08-11

We report on DNA translocations through nanopores created in graphene membranes. Devices consist of 1-5 nm thick graphene membranes with electron-beam sculpted nanopores from 5 to 10 nm in diameter. Due to the thin nature of the graphene membranes, we observe larger blocked currents than for traditional solid-state nanopores. However, ionic current noise levels are several orders of magnitude larger than those for silicon nitride nanopores. These fluctuations are reduced with the atomic-layer deposition of 5 nm of titanium dioxide over the device. Unlike traditional solid-state nanopore materials that are insulating, graphene is an excellent electrical conductor. Use of graphene as a membrane material opens the door to a new class of nanopore devices in which electronic sensing and control are performed directly at the pore.

Structure-dependent water transport across nanopores of carbon nanotubes: toward selective gating upon temperature regulation.

PubMed

Zhao, Kuiwen; Wu, Huiying

2015-04-28

Determining water structure in nanopores and its influence on water transport behaviour is of great importance for understanding and regulating the transport across nanopores. Here we report an ultrafast-slow flow transition phenomenon for water transport across nanopores of carbon nanotubes owing to the change in water structure in nanopores induced by temperature. By performing extensive molecular dynamics simulations, we show the dependence of water transport behaviours on water structures. Our results indicate that owing to the change in water structure in nanopores, water flux across nanopores with certain pore sizes decreases sharply (nearly 3 orders of magnitude) with the decreasing temperature. This phenomenon is very sensitive to the pore size. The threshold temperatures for the occurrence of the ultrafast-slow flow transition for water transport are also determined for various pore sizes. These findings suggest a novel protocol for selective gating of water and proton conduction across nanopores and temperature-controlled drug release.

Nanopore-CMOS Interfaces for DNA Sequencing

PubMed Central

Magierowski, Sebastian; Huang, Yiyun; Wang, Chengjie; Ghafar-Zadeh, Ebrahim

2016-01-01

DNA sequencers based on nanopore sensors present an opportunity for a significant break from the template-based incumbents of the last forty years. Key advantages ushered by nanopore technology include a simplified chemistry and the ability to interface to CMOS technology. The latter opportunity offers substantial promise for improvement in sequencing speed, size and cost. This paper reviews existing and emerging means of interfacing nanopores to CMOS technology with an emphasis on massively-arrayed structures. It presents this in the context of incumbent DNA sequencing techniques, reviews and quantifies nanopore characteristics and models and presents CMOS circuit methods for the amplification of low-current nanopore signals in such interfaces. PMID:27509529

Nanopore-CMOS Interfaces for DNA Sequencing.

PubMed

Magierowski, Sebastian; Huang, Yiyun; Wang, Chengjie; Ghafar-Zadeh, Ebrahim

2016-08-06

DNA sequencers based on nanopore sensors present an opportunity for a significant break from the template-based incumbents of the last forty years. Key advantages ushered by nanopore technology include a simplified chemistry and the ability to interface to CMOS technology. The latter opportunity offers substantial promise for improvement in sequencing speed, size and cost. This paper reviews existing and emerging means of interfacing nanopores to CMOS technology with an emphasis on massively-arrayed structures. It presents this in the context of incumbent DNA sequencing techniques, reviews and quantifies nanopore characteristics and models and presents CMOS circuit methods for the amplification of low-current nanopore signals in such interfaces.

Nanochannel Device with Embedded Nanopore: a New Approach for Single-Molecule DNA Analysis and Manipulation

NASA Astrophysics Data System (ADS)

Zhang, Yuning; Reisner, Walter

2013-03-01

Nanopore and nanochannel based devices are robust methods for biomolecular sensing and single DNA manipulation. Nanopore-based DNA sensing has attractive features that make it a leading candidate as a single-molecule DNA sequencing technology. Nanochannel based extension of DNA, combined with enzymatic or denaturation-based barcoding schemes, is already a powerful approach for genome analysis. We believe that there is revolutionary potential in devices that combine nanochannels with embedded pore detectors. In particular, due to the fast translocation of a DNA molecule through a standard nanopore configuration, there is an unfavorable trade-off between signal and sequence resolution. With a combined nanochannel-nanopore device, based on embedding a pore inside a nanochannel, we can in principle gain independent control over both DNA translocation speed and sensing signal, solving the key draw-back of the standard nanopore configuration. We demonstrate that we can optically detect successful translocation of DNA from the nanochannel out through the nanopore, a possible method to 'select' a given barcode for further analysis. In particular, we show that in equilibrium DNA will not escape through an embedded sub-persistence length nanopore, suggesting that the pore could be used as a nanoscale window through which to interrogate a nanochannel extended DNA molecule. Furthermore, electrical measurements through the nanopore are performed, indicating that DNA sensing is feasible using the nanochannel-nanopore device.

Optofluidic devices with integrated solid-state nanopores

PubMed Central

Hawkins, Aaron R.; Schmidt, Holger

2016-01-01

This review (with 90 refs.) covers the state of the art in optofluidic devices with integrated solid-state nanopores for use in detection and sensing. Following an introduction into principles of optofluidics and solid-state nanopore technology, we discuss features of solid-state nanopore based assays using optofluidics. This includes the incorporation of solid-state nanopores into optofluidic platforms based on liquid-core anti-resonant reflecting optical waveguides (ARROWs), methods for their fabrication, aspects of single particle detection and particle manipulation. We then describe the new functionalities provided by solid-state nanopores integrated into optofluidic chips, in particular acting as smart gates for correlated electro-optical detection and discrimination of nanoparticles. This enables the identification of viruses and λ-DNA, particle trajectory simulations, enhancing sensitivity by tuning the shape of nanopores. The review concludes with a summary and an outlook. PMID:27046940

Nanoporous frameworks exhibiting multiple stimuli responsiveness

NASA Astrophysics Data System (ADS)

Kundu, Pintu K.; Olsen, Gregory L.; Kiss, Vladimir; Klajn, Rafal

2014-04-01

Nanoporous frameworks are polymeric materials built from rigid molecules, which give rise to their nanoporous structures with applications in gas sorption and storage, catalysis and others. Conceptually new applications could emerge, should these beneficial properties be manipulated by external stimuli in a reversible manner. One approach to render nanoporous frameworks responsive to external signals would be to immobilize molecular switches within their nanopores. Although the majority of molecular switches require conformational freedom to isomerize, and switching in the solid state is prohibited, the nanopores may provide enough room for the switches to efficiently isomerize. Here we describe two families of nanoporous materials incorporating the spiropyran molecular switch. These materials exhibit a variety of interesting properties, including reversible photochromism and acidochromism under solvent-free conditions, light-controlled capture and release of metal ions, as well reversible chromism induced by solvation/desolvation.

Solid-state nanopores of controlled geometry fabricated in a transmission electron microscope

NASA Astrophysics Data System (ADS)

Qian, Hui; Egerton, Ray F.

2017-11-01

Energy-filtered transmission electron microscopy and electron tomography were applied to in situ studies of the formation, shape, and diameter of nanopores formed in a silicon nitride membrane in a transmission electron microscope. The nanopore geometry was observed in three dimensions by electron tomography. Drilling conditions, such as probe current, beam convergence angle, and probe position, affect the formation rate and the geometry of the pores. With a beam convergence semi-angle of α = 22 mrad, a conical shaped nanopore is formed but at α = 45 mrad, double-cone (hourglass-shaped) nanopores were produced. Nanopores with an effective diameter between 10 nm and 1.8 nm were fabricated by controlling the drilling time.

Ion transport by gating voltage to nanopores produced via metal-assisted chemical etching method

NASA Astrophysics Data System (ADS)

Van Toan, Nguyen; Inomata, Naoki; Toda, Masaya; Ono, Takahito

2018-05-01

In this work, we report a simple and low-cost way to create nanopores that can be employed for various applications in nanofluidics. Nano sized Ag particles in the range from 1 to 20 nm are formed on a silicon substrate with a de-wetting method. Then the silicon nanopores with an approximate 15 nm average diameter and 200 μm height are successfully produced by the metal-assisted chemical etching method. In addition, electrically driven ion transport in the nanopores is demonstrated for nanofluidic applications. Ion transport through the nanopores is observed and could be controlled by an application of a gating voltage to the nanopores.

Ion transport by gating voltage to nanopores produced via metal-assisted chemical etching method.

PubMed

Van Toan, Nguyen; Inomata, Naoki; Toda, Masaya; Ono, Takahito

2018-05-11

In this work, we report a simple and low-cost way to create nanopores that can be employed for various applications in nanofluidics. Nano sized Ag particles in the range from 1 to 20 nm are formed on a silicon substrate with a de-wetting method. Then the silicon nanopores with an approximate 15 nm average diameter and 200 μm height are successfully produced by the metal-assisted chemical etching method. In addition, electrically driven ion transport in the nanopores is demonstrated for nanofluidic applications. Ion transport through the nanopores is observed and could be controlled by an application of a gating voltage to the nanopores.

Effect of pH on ion current through conical nanopores

NASA Astrophysics Data System (ADS)

Chander, M.; Kumar, R.; Kumar, S.; Kumar, N.

2018-05-01

Here, we examined ionic current behavior of conical nanopores at different pH and a fixed ion concentration of potassium halide (KCl). Conical shaped nanopores have been developed by chemical etching technique in polyethylene terephthalate (PET) membrane/foil of thickness 12 micron. For this we employed a self-assembled electrochemical cell having two chambers and the foil was fitted in the centre of cell. The nanopores were produced in the foil using etching and stopping solutions. The experimental results show that ionic current rectification (ICR) occurs through synthesized conical nanopores. Further, ion current increases significantly with increase of voltage from the base side of nanopores to the tip side at fixed pH of electrolyte.

Recent patents of nanopore DNA sequencing technology: progress and challenges.

PubMed

Zhou, Jianfeng; Xu, Bingqian

2010-11-01

DNA sequencing techniques witnessed fast development in the last decades, primarily driven by the Human Genome Project. Among the proposed new techniques, Nanopore was considered as a suitable candidate for the single DNA sequencing with ultrahigh speed and very low cost. Several fabrication and modification techniques have been developed to produce robust and well-defined nanopore devices. Many efforts have also been done to apply nanopore to analyze the properties of DNA molecules. By comparing with traditional sequencing techniques, nanopore has demonstrated its distinctive superiorities in main practical issues, such as sample preparation, sequencing speed, cost-effective and read-length. Although challenges still remain, recent researches in improving the capabilities of nanopore have shed a light to achieve its ultimate goal: Sequence individual DNA strand at single nucleotide level. This patent review briefly highlights recent developments and technological achievements for DNA analysis and sequencing at single molecule level, focusing on nanopore based methods.

Single nanopore transport of synthetic and biological polyelectrolytes in three-dimensional hybrid microfluidic/nanofluidic devices

DOE PAGES

King, Travis L.; Gatimu, Enid N.; Bohn, Paul W.

2009-01-02

This paper presents a study of electrokinetic transport in single nanopores integrated into vertically-stacked three-dimensional hybrid microfluidic/nanofluidic structures. In these devices single nanopores, created by focused ion beam (FIB) milling in thin polymer films, provide fluidic connection between two vertically separated, perpendicular microfluidic channels. Experiments address both systems in which the nanoporous membrane is composed of the same (homojunction) or different (heterojunction) polymer as the microfluidic channels. These devices are then used to study the electrokinetic transport properties of synthetic (i.e., polystyrene sulfonate and polyallylamine) and biological (i.e.,DNA) polyelectrolytes across these nanopores. Single nanopore transport of polyelectrolytes across these nanoporesmore » using both electrical current measurements and confocal microscopy. Both optical and electrical measurements indicate that electroosmotic transport is predominant over electrophoresis in single nanopores with d > 180 nm, consistent with results obtained under similar conditions for nanocapillary array membranes.« less

Na⁺ and K⁺ ion selectivity by size-controlled biomimetic graphene nanopores.

PubMed

Kang, Yu; Zhang, Zhisen; Shi, Hui; Zhang, Junqiao; Liang, Lijun; Wang, Qi; Ågren, Hans; Tu, Yaoquan

2014-09-21

Because biological ionic channels play a key role in cellular transport phenomena, they have attracted extensive research interest for the design of biomimetic nanopores with high permeability and selectivity in a variety of technical applications. Inspired by the structure of K(+) channel proteins, we designed a series of oxygen doped graphene nanopores of different sizes by molecular dynamics simulations to discriminate between K(+) and Na(+) channel transport. The results from free energy calculations indicate that the ion selectivity of such biomimetic graphene nanopores can be simply controlled by the size of the nanopore; compared to K(+), the smaller radius of Na(+) leads to a significantly higher free energy barrier in the nanopore of a certain size. Our results suggest that graphene nanopores with a distance of about 3.9 Å between two neighboring oxygen atoms could constitute a promising candidate to obtain excellent ion selectivity for Na(+) and K(+) ions.

Alumina plate containing photosystem I reaction center complex oriented inside plate-penetrating silica nanopores.

PubMed

Kamidaki, Chihiro; Kondo, Toru; Noji, Tomoyasu; Itoh, Tetsuji; Yamaguchi, Akira; Itoh, Shigeru

2013-08-22

The photosynthetic photosystem I reaction center complex (PSI-RC), which has a molecular diameter of 21 nm with 100 pigments, was incorporated into silica nanopores with a 100-nm diameter that penetrates an alumina plate of 60-μm thickness to make up an inorganic-biological hybrid photocell. PSI-RCs, purified from a thermophilic cyanobacterium, were stable inside the nanopores and rapidly photoreduced a mediator dye methyl viologen. The reduced dye was more stable inside nanopores suggesting the decrease of dissolved oxygen. The analysis by a cryogenic electron spin paramagnetic resonance indicated the oriented arrangement of RCs inside the 100-nm nanopores, with their surface parallel to the silica wall and perpendicular to the plane of the alumina plate. PSI RC complex in the semicrystalline orientation inside silica nanopores can be a new type of light energy conversion unit to supply strong reducing power selectively to other molecules inside or outside nanopores.

In situ heavy ion irradiation studies of nanopore shrinkage and enhanced radiation tolerance of nanoporous Au

DOE PAGES

Li, Jin; Fan, Cuncai; Ding, Jie; ...

2017-01-03

High energy particle radiations induce severe microstructural damage in metallic materials. Nanoporous materials with a giant surface-to-volume ratio may alleviate radiation damage in irradiated metallic materials as free surface are defect sinks. We show, by using in situ Kr ion irradiation in a transmission electron microscope at room temperature, that nanoporous Au indeed has significantly improved radiation tolerance comparing with coarse-grained, fully dense Au. In situ studies show that nanopores can absorb and eliminate a large number of radiation-induced defect clusters. Meanwhile, nanopores shrink (self-heal) during radiation, and their shrinkage rate is pore size dependent. Furthermore, the in situ studiesmore » show dose-rate-dependent diffusivity of defect clusters. Our study sheds light on the design of radiation-tolerant nanoporous metallic materials for advanced nuclear reactor applications.« less

Highly active thermally stable nanoporous gold catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biener, Juergen; Wittstock, Arne; Biener, Monika M.

In one embodiment, a system includes a nanoporous gold structure and a plurality of oxide particles deposited on the nanoporous gold structure; the oxide particles are characterized by a crystalline phase. In another embodiment, a method includes depositing oxide nanoparticles on a nanoporous gold support to form an active structure and functionalizing the deposited oxide nanoparticles.

Development of a 3D origami multiplex electrochemical immunodevice using a nanoporous silver-paper electrode and metal ion functionalized nanoporous gold-chitosan.

PubMed

Li, Weiping; Li, Long; Li, Meng; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

2013-10-25

A simple and sensitive 3D microfluidic origami multiplex electrochemical immunodevice was developed for the first time using a novel nanoporous silver modified paper working electrode as a sensor platform and different metal ion functionalized nanoporous gold-chitosan as a tracer.

Basic evaluation of typical nanoporous silica nanoparticles in being drug carrier: Structure, wettability and hemolysis.

PubMed

Li, Jing; Guo, Yingyu

2017-04-01

Herein, the present work devoted to study the basic capacity of nanoporous silica nanoparticles in being drug carrier that covered structure, wettability and hemolysis so as to provide crucial evaluation. Typical nanoporous silica nanoparticles that consist of nanoporous silica nanoparticles (NSN), amino modified nanoporous silica nanoparticles (amino-NSN), carboxyl modified nanoporous silica nanoparticles (carboxyl-NSN) and hierachical nanoporous silica nanoparticles (hierachical-NSN) were studied. The results showed that their wettability and hemolysis were closely related to structure and surface modification. Basically, wettability became stronger as the amount of OH on the surface of NSN was higher. Both large nanopores and surface modification can reduce the wettability of NSN. Furthermore, NSN series were safe to be used when they circulated into the blood in low concentration, while if high concentration can not be avoided during administration, high porosity or amino modification of NSN were safer to be considered. It is believed that the basic evaluation of NSN can make contribution in providing scientific instruction for designing drug loaded NSN systems. Copyright © 2016 Elsevier B.V. All rights reserved.

Precise fabrication of a 5 nm graphene nanopore with a helium ion microscope for biomolecule detection

NASA Astrophysics Data System (ADS)

Deng, Yunsheng; Huang, Qimeng; Zhao, Yue; Zhou, Daming; Ying, Cuifeng; Wang, Deqiang

2017-01-01

We report a scalable method to fabricate high-quality graphene nanopores for biomolecule detection using a helium ion microscope (HIM). HIM milling shows promising capabilities for precisely controlling the size and shape, and may allow for the potential production of nanopores at wafer scale. Nanopores could be fabricated at different sizes ranging from 5 to 30 nm in diameter in few minutes. Compared with the current solid-state nanopore fabrication techniques, e.g. transmission electron microscopy, HIM is fast. Furthermore, we investigated the exposure-time dependence of graphene nanopore formation: the rate of pore expansion did not follow a simple linear relationship with exposure time, but a fast expansion rate at short exposure time and a slow rate at long exposure time. In addition, we performed biomolecule detection with our patterned graphene nanopore. The ionic current signals induced by 20-base single-stranded DNA homopolymers could be used as a basis for homopolymer differentiation. However, the charge interaction of homopolymer chains with graphene nanopores, and the conformations of homopolymer chains need to be further considered to improve the accuracy of discrimination.

Measurement of DNA translocation dynamics in a solid-state nanopore at 100-ns temporal resolution

PubMed Central

Shekar, Siddharth; Niedzwiecki, David J.; Chien, Chen-Chi; Ong, Peijie; Fleischer, Daniel A.; Lin, Jianxun; Rosenstein, Jacob K.; Drndic, Marija; Shepard, Kenneth L.

2017-01-01

Despite the potential for nanopores to be a platform for high-bandwidth study of single-molecule systems, ionic current measurements through nanopores have been limited in their temporal resolution by noise arising from poorly optimized measurement electronics and large parasitic capacitances in the nanopore membranes. Here, we present a complementary metal-oxide-semiconductor (CMOS) nanopore (CNP) amplifier capable of low noise recordings at an unprecedented 10 MHz bandwidth. When integrated with state-of-the-art solid-state nanopores in silicon nitride membranes, we achieve an SNR of greater than 10 for ssDNA translocations at a measurement bandwidth of 5 MHz, which represents the fastest ion current recordings through nanopores reported to date. We observe transient features in ssDNA translocation events that are as short as 200 ns, which are hidden even at bandwidths as high as 1 MHz. These features offer further insights into the translocation kinetics of molecules entering and exiting the pore. This platform highlights the advantages of high-bandwidth translocation measurements made possible by integrating nanopores and custom-designed electronics. PMID:27332998

Nanofluidic Device with Embedded Nanopore

NASA Astrophysics Data System (ADS)

Zhang, Yuning; Reisner, Walter

2014-03-01

Nanofluidic based devices are robust methods for biomolecular sensing and single DNA manipulation. Nanopore-based DNA sensing has attractive features that make it a leading candidate as a single-molecule DNA sequencing technology. Nanochannel based extension of DNA, combined with enzymatic or denaturation-based barcoding schemes, is already a powerful approach for genome analysis. We believe that there is revolutionary potential in devices that combine nanochannels with nanpore detectors. In particular, due to the fast translocation of a DNA molecule through a standard nanopore configuration, there is an unfavorable trade-off between signal and sequence resolution. With a combined nanochannel-nanopore device, based on embedding a nanopore inside a nanochannel, we can in principle gain independent control over both DNA translocation speed and sensing signal, solving the key draw-back of the standard nanopore configuration. We demonstrate that we can detect - using fluorescent microscopy - successful translocation of DNA from the nanochannel out through the nanopore, a possible method to 'select' a given barcode for further analysis. We also show that in equilibrium DNA will not escape through an embedded sub-persistence length nanopore until a certain voltage bias is added.

3-D simulation of nanopore structure for DNA sequencing.

PubMed

Park, Jun-Mo; Pak, Y Eugene; Chun, Honggu; Lee, Jong-Ho

2012-07-01

In this paper, we propose a method for simulating nanopore structure by using conventional 3-D simulation tool to mimic the I-V behavior of the nanopore structure. In the simulation, we use lightly doped silicon for ionic solution where some parameters like electron affinity and dielectric constant are fitted to consider the ionic solution. By using this method, we can simulate the I-V behavior of nanopore structure depending on the location and the size of the sphere shaped silicon oxide which is considered to be an indicator of a DNA base. In addition, we simulate an Ionic Field Effect Transistor (IFET) which has basically the nanopore structure, and show that the simulated curves follow sufficiently the I-V behavior of the measurement data. Therefore, we think it is reasonable to apply parameter modeling mentioned above to simulate nanopore structure. The key idea is to modify electron affinity of silicon which is used to mimic the KCl solution to avoid band bending and depletion inside the nanopore. We could efficiently utilize conventional 3-D simulation tool to simulate the I-V behavior of nanopore structures.

Ion selection of charge-modified large nanopores in a graphene sheet

NASA Astrophysics Data System (ADS)

Zhao, Shijun; Xue, Jianming; Kang, Wei

2013-09-01

Water desalination becomes an increasingly important approach for clean water supply to meet the rapidly growing demand of population boost, industrialization, and urbanization. The main challenge in current desalination technologies lies in the reduction of energy consumption and economic costs. Here, we propose to use charged nanopores drilled in a graphene sheet as ion exchange membranes to promote the efficiency and capacity of desalination systems. Using molecular dynamics simulations, we investigate the selective ion transport behavior of electric-field-driven KCl electrolyte solution through charge modified graphene nanopores. Our results reveal that the presence of negative charges at the edge of graphene nanopore can remarkably impede the passage of Cl- while enhance the transport of K+, which is an indication of ion selectivity for electrolytes. We further demonstrate that this selectivity is dependent on the pore size and total charge number assigned at the nanopore edge. By adjusting the nanopore diameter and electric charge on the graphene nanopore, a nearly complete rejection of Cl- can be realized. The electrical resistance of nanoporous graphene, which is a key parameter to evaluate the performance of ion exchange membranes, is found two orders of magnitude lower than commercially used membranes. Our results thus suggest that graphene nanopores are promising candidates to be used in electrodialysis technology for water desalinations with a high permselectivity.

Selective Separation of Metal Ions via Monolayer Nanoporous Graphene with Carboxyl Groups.

PubMed

Li, Zhan; Liu, Yanqi; Zhao, Yang; Zhang, Xin; Qian, Lijuan; Tian, Longlong; Bai, Jing; Qi, Wei; Yao, Huijun; Gao, Bin; Liu, Jie; Wu, Wangsuo; Qiu, Hongdeng

2016-10-18

Graphene-coated plastic substrates, such as polyethylene terephthalate (PET), are regularly used in flexible electronic devices. Here we demonstrate a new application of the graphene-coated nanoporous PET membrane for the selective separation of metal ions in an ion exchange manner. Irradiation with swift heavy ions is used to perforate graphene and PET substrate. This process could create graphene nanopores with carboxyl groups, thus forming conical holes in the PET after chemical etching to support graphene nanopores. Therefore, a monolayer nanoporous graphene membrane with a PET substrate is constructed successfully to investigate its ionic selective separation. We find that the permeation ratio of ions strongly depends on the temperature and H + concentration in the driving solution. An electric field can increase the permeation ratio of ions through the graphene nanopores, but it inhibits the ion selective separation. Moreover, the structure of the graphene nanopore with carboxyl groups is resolved at the density functional theory level. The results show the asymmetric structure of the nanopore with carboxyl groups, and the analysis indicates that the ionic permeation can be attributed to the ion exchange between metal ions and protons on the two sides of graphene nanopores. These results would be beneficial to the design of membrane separation materials made from graphene with efficient online and offline bulk separation.

Micropatterning of a nanoporous alumina membrane with poly(ethylene glycol) hydrogel to create cellular micropatterns on nanotopographic substrates.

PubMed

Lee, Hyun Jong; Kim, Dae Nyun; Park, Saemi; Lee, Yeol; Koh, Won-Gun

2011-03-01

In this paper, we describe a simple method for fabricating micropatterned nanoporous substrates that are capable of controlling the spatial positioning of mammalian cells. Micropatterned substrates were prepared by fabricating poly(ethylene glycol) (PEG) hydrogel microstructures on alumina membranes with 200 nm nanopores using photolithography. Because hydrogel precursor solution could infiltrate and become crosslinked within the nanopores, the resultant hydrogel micropatterns were firmly anchored on the substrate without the use of adhesion-promoting monolayers, thereby allow tailoring of the surface properties of unpatterned nanoporous areas. For mammalian cell patterning, arrays of microwells of different dimensions were fabricated. These microwells were composed of hydrophilic PEG hydrogel walls surrounding nanoporous bottoms that were modified with cell-adhesive Arg-Gly-Asp (RGD) peptides. Because the PEG hydrogel was non-adhesive towards proteins and cells, cells adhered selectively and remained viable within the RGD-modified nanoporous regions, thereby creating cellular micropatterns. Although the morphology of cell clusters and the number of cells inside one microwell were dependent on the lateral dimension of the microwells, adhered cells that were in direct contact with nanopores were able to penetrate into the nanopores by small extensions (filopodia) for all the different sizes of microwells evaluated. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework.

PubMed

Salunkhe, Rahul R; Tang, Jing; Kamachi, Yuichiro; Nakato, Teruyuki; Kim, Jung Ho; Yamauchi, Yusuke

2015-06-23

Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal-organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2)·g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2)·g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F·g(-1), respectively, at a scan rate of 5 mV·s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the ASC (Co3O4//carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed ASC with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W·h·kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W·kg(-1) at a specific energy of 15 W·h·kg(-1)) combined with long-term stability up to 2000 cycles.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Improved Analysis of Nanopore Sequence Data and Scanning Nanopore Techniques

NASA Astrophysics Data System (ADS)

Szalay, Tamas

The field of nanopore research has been driven by the need to inexpensively and rapidly sequence DNA. In order to help realize this goal, this thesis describes the PoreSeq algorithm that identifies and corrects errors in real-world nanopore sequencing data and improves the accuracy of de novo genome assembly with increasing coverage depth. The approach relies on modeling the possible sources of uncertainty that occur as DNA advances through the nanopore and then using this model to find the sequence that best explains multiple reads of the same region of DNA. PoreSeq increases nanopore sequencing read accuracy of M13 bacteriophage DNA from 85% to 99% at 100X coverage. We also use the algorithm to assemble E. coli with 30X coverage and the lambda genome at a range of coverages from 3X to 50X. Additionally, we classify sequence variants at an order of magnitude lower coverage than is possible with existing methods. This thesis also reports preliminary progress towards controlling the motion of DNA using two nanopores instead of one. The speed at which the DNA travels through the nanopore needs to be carefully controlled to facilitate the detection of individual bases. A second nanopore in close proximity to the first could be used to slow or stop the motion of the DNA in order to enable a more accurate readout. The fabrication process for a new pyramidal nanopore geometry was developed in order to facilitate the positioning of the nanopores. This thesis demonstrates that two of them can be placed close enough to interact with a single molecule of DNA, which is a prerequisite for being able to use the driving force of the pores to exert fine control over the motion of the DNA. Another strategy for reading the DNA is to trap it completely with one pore and to move the second nanopore instead. To that end, this thesis also shows that a single strand of immobilized DNA can be captured in a scanning nanopore and examined for a full hour, with data from many scans at many different voltages obtained in order to detect a bound protein placed partway along the molecule.

WS2 nanopores for molecule analysis

NASA Astrophysics Data System (ADS)

Danda, Gopinath; Masih Das, Paul; Chou, Yung-Chien; Mlack, Jerome; Naylor, Carl; Perea-Lopez, Nestor; Lin, Zhong; Fulton, Laura Beth; Terrones, Mauricio; Johnson, A. T. Charlie; Drndic, Marija

Atomically thin 2D materials like graphene and transition metal dichalcogenides (TMDs) are interesting as membranes in solid state nanopore sensors for DNA analysis as they may facilitate single base resolution sequencing. These materials also exhibit unique optical and electronic properties which may be exploited to enhance the functionality of nanopore sensors. Here, we report WS2 nanopores, fabricated using a focused TEM beam. We also report their controlled laser-induced expansion in ionic solution. This study demonstrates the possibility of dynamic control of nanopore characteristics optically. NIH Grant R21HG007856, NSF EFRI-1542707.

Fabricatable nanopore sensors with an atomic thickness

NASA Astrophysics Data System (ADS)

Luan, Binquan; Bai, Jingwei; Stolovitzky, Gustavo

2013-10-01

When analyzing biological molecules (such as DNA and proteins) transported through a nanopore sensor, the pore length limits both the sensitivity and the spatial resolution. Atomically thin as a graphene nanopore is, it is difficult to make graphene pores and the scalable-fabrication of those pores has not yet been possible. We theoretically studied a type of atomically thin nanopores that are formed by intersection of two perpendicular nano-slits. Based on theoretical analyses, we demonstrate that slit nanopores behave similarly to graphene pores and can be manufactured at a wafer scale.

Nanopores formed by DNA origami: a review.

PubMed

Bell, Nicholas A W; Keyser, Ulrich F

2014-10-01

Nanopores have emerged over the past two decades to become an important technique in single molecule experimental physics and biomolecule sensing. Recently DNA nanotechnology, in particular DNA origami, has been used for the formation of nanopores in insulating materials. DNA origami is a very attractive technique for the formation of nanopores since it enables the construction of 3D shapes with precise control over geometry and surface functionality. DNA origami has been applied to nanopore research by forming hybrid architectures with solid state nanopores and by direct insertion into lipid bilayers. This review discusses recent experimental work in this area and provides an outlook for future avenues and challenges. Copyright © 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Single Nanoparticle Translocation Through Chemically Modified Solid Nanopore

NASA Astrophysics Data System (ADS)

Tan, Shengwei; Wang, Lei; Liu, Hang; Wu, Hongwen; Liu, Quanjun

2016-02-01

The nanopore sensor as a high-throughput and low-cost technology can detect single nanoparticle in solution. In the present study, the silicon nitride nanopores were fabricated by focused Ga ion beam (FIB), and the surface was functionalized with 3-aminopropyltriethoxysilane to change its surface charge density. The positively charged nanopore surface attracted negatively charged nanoparticles when they were in the vicinity of the nanopore. And, nanoparticle translocation speed was slowed down to obtain a clear and deterministic signal. Compared with previous studied small nanoparticles, the electrophoretic translocation of negatively charged polystyrene (PS) nanoparticles (diameter ~100 nm) was investigated in solution using the Coulter counter principle in which the time-dependent nanopore current was recorded as the nanoparticles were driven across the nanopore. A linear dependence was found between current drop and biased voltage. An exponentially decaying function ( t d ~ e -v/v0 ) was found between the duration time and biased voltage. The interaction between the amine-functionalized nanopore wall and PS microspheres was discussed while translating PS microspheres. We explored also translocations of PS microspheres through amine-functionalized solid-state nanopores by varying the solution pH (5.4, 7.0, and 10.0) with 0.02 M potassium chloride (KCl). Surface functionalization showed to provide a useful step to fine-tune the surface property, which can selectively transport molecules or particles. This approach is likely to be applied to gene sequencing.

SEM-induced shrinkage and site-selective modification of single-crystal silicon nanopores

NASA Astrophysics Data System (ADS)

Chen, Qi; Wang, Yifan; Deng, Tao; Liu, Zewen

2017-07-01

Solid-state nanopores with feature sizes around 5 nm play a critical role in bio-sensing fields, especially in single molecule detection and sequencing of DNA, RNA and proteins. In this paper we present a systematic study on shrinkage and site-selective modification of single-crystal silicon nanopores with a conventional scanning electron microscope (SEM). Square nanopores with measurable sizes as small as 8 nm × 8 nm and rectangle nanopores with feature sizes (the smaller one between length and width) down to 5 nm have been obtained, using the SEM-induced shrinkage technique. The analysis of energy dispersive x-ray spectroscopy and the recovery of the pore size and morphology reveal that the grown material along with the edge of the nanopore is the result of deposition of hydrocarbon compounds, without structural damage during the shrinking process. A simplified model for pore shrinkage has been developed based on observation of the cross-sectional morphology of the shrunk nanopore. The main factors impacting on the task of controllably shrinking the nanopores, such as the accelerating voltage, spot size, scanned area of e-beam, and the initial pore size have been discussed. It is found that single-crystal silicon nanopores shrink linearly with time under localized irradiation by SEM e-beam in all cases, and the pore shrinkage rate is inversely proportional to the initial equivalent diameter of the pore under the same e-beam conditions.

Nanochannel Device with Embedded Nanopore: a New Approach for Single-Molecule DNA Analysis and Manipulation

NASA Astrophysics Data System (ADS)

Zhang, Yuning; Reisner, Walter

2012-02-01

Nanopore and nanochannel based devices are robust methods for biomolecular sensing and single DNA manipulation. Nanopore-based DNA sensing has attractive features that make it a leading candidate as a single-molecule DNA sequencing technology. Nanochannel based extension of DNA, combined with enzymatic or denaturation-based barcoding schemes, is already a powerful approach for genome analysis. We believe that there is revolutionary potential in devices that combine nanochannels with nanpore detectors. In particular, due to the fast translocation of a DNA molecule through a standard nanopore configuration, there is an unfavorable trade-off between signal and sequence resolution. With a combined nanochannel-nanopore device, based on embedding a nanopore inside a nanochannel, we can in principle gain independent control over both DNA translocation speed and sensing signal, solving the key draw-back of the standard nanopore configuration. We will discuss our recent progress on device fabrication and characterization. In particular, we demonstrate that we can detect - using fluorescent microscopy - successful translocation of DNA from the nanochannel out through the nanopore, a possible method to 'select' a given barcode for further analysis. In particular, we show that in equilibrium DNA will not escape through an embedded sub-persistence length nanopore, suggesting that the embedded pore could be used as a nanoscale window through which to interrogate a nanochannel extended DNA molecule.

Using Synthetic Nanopores for Single-Molecule Analyses: Detecting SNPs, Trapping DNA Molecules, and the Prospects for Sequencing DNA

ERIC Educational Resources Information Center

Dimitrov, Valentin V.

2009-01-01

This work focuses on studying properties of DNA molecules and DNA-protein interactions using synthetic nanopores, and it examines the prospects of sequencing DNA using synthetic nanopores. We have developed a method for discriminating between alleles that uses a synthetic nanopore to measure the binding of a restriction enzyme to DNA. There exists…

Modeling electrochemical deposition inside nanotubes to obtain metal-semiconductor multiscale nanocables or conical nanopores.

PubMed

Lebedev, Konstantin; Mafé, Salvador; Stroeve, Pieter

2005-08-04

Nanocables with a radial metal-semiconductor heterostructure have recently been prepared by electrochemical deposition inside metal nanotubes. First, a bare nanoporous polycarbonate track-etched membrane is coated uniformly with a metal film by electroless deposition. The film forms a working electrode for further deposition of a semiconductor layer that grows radially inside the nanopore when the deposition rate is slow. We propose a new physical model for the nanocable synthesis and study the effects of the deposited species concentration, potential-dependent reaction rate, and nanopore dimensions on the electrochemical deposition. The problem involves both axial diffusion through the nanopore and radial transport to the nanopore surface, with a surface reaction rate that depends on the axial position and the time. This is so because the radial potential drop across the deposited semiconductor layer changes with the layer thickness through the nanopore. Since axially uniform nanocables are needed for most applications, we consider the relative role of reaction and axial diffusion rates on the deposition process. However, in those cases where partial, empty-core deposition should be desirable (e.g., for producing conical nanopores to be used in single nanoparticle detection), we give conditions where asymmetric geometries can be experimentally realized.

Thermal conductivity model for nanoporous thin films

NASA Astrophysics Data System (ADS)

Huang, Congliang; Zhao, Xinpeng; Regner, Keith; Yang, Ronggui

2018-03-01

Nanoporous thin films have attracted great interest because of their extremely low thermal conductivity and potential applications in thin thermal insulators and thermoelectrics. Although there are some numerical and experimental studies about the thermal conductivity of nanoporous thin films, a simplified model is still needed to provide a straightforward prediction. In this paper, by including the phonon scattering lifetimes due to film thickness boundary scattering, nanopore scattering and the frequency-dependent intrinsic phonon-phonon scattering, a fitting-parameter-free model based on the kinetic theory of phonon transport is developed to predict both the in-plane and the cross-plane thermal conductivities of nanoporous thin films. With input parameters such as the lattice constants, thermal conductivity, and the group velocity of acoustic phonons of bulk silicon, our model shows a good agreement with available experimental and numerical results of nanoporous silicon thin films. It illustrates that the size effect of film thickness boundary scattering not only depends on the film thickness but also on the size of nanopores, and a larger nanopore leads to a stronger size effect of the film thickness. Our model also reveals that there are different optimal structures for getting the lowest in-plane and cross-plane thermal conductivities.

Single Protein Structural Analysis with a Solid-state Nanopore Sensor

NASA Astrophysics Data System (ADS)

Li, Jiali; Golovchenko, Jene; McNabb, David

2005-03-01

We report on the use of solid-state nanopore sensors to detect single polypeptides. These solid-state nanopores are fabricated in thin membranes of silicon nitride by ion beam sculpting...[1]. When an electrically biased nanopore is exposed to denatured proteins in ionic solution, discrete transient electronic signals: current blockages are observed. We demonstrate examples of such transient electronic signals for Bovine Serum Albumin (BSA) and human placental laminin M proteins in Guanidine hydrochloride solution, which suggest that these polypeptides are individually translocating through the nanopore during the detecting process. The amplitude of the current blockages is proportional to the bias voltage. No transient current blockages are observed when proteins are not present in the solution. To probe protein-folding state, pH and temperature dependence experiments are performed. The results demonstrate a solid-state nanopore sensor can be used to detect and analyze single polypeptide chains. Similarities and differences with signals obtained from double stranded DNA in a solid-state nanopore and single stranded DNA in a biological nanopore are discussed. [.1] Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169.

Length-dependent corrosion behavior, Ni2+ release, cytocompatibility, and antibacterial ability of Ni-Ti-O nanopores anodically grown on biomedical NiTi alloy.

PubMed

Hang, Ruiqiang; Liu, Yanlian; Bai, Long; Zhang, Xiangyu; Huang, Xiaobo; Jia, Husheng; Tang, Bin

2018-08-01

In the present work, nickel-titanium-oxygen nanopores with different length (0.55-114 μm) were anodically grown on nearly equiatomic nickel-titanium (NiTi) alloy. Length-dependent corrosion behavior, nickel ion (Ni 2+ ) release, cytocompatibility, and antibacterial ability were investigated by electrochemical, analytical chemistry, and biological methods. The results show constructing nanoporous structure on the NiTi alloy improve its corrosion resistance. However, the anodized samples release more Ni 2+ than that of the bare NiTi alloy, suggesting chemical dissolution of the nanopores rather than electrochemical corrosion governs the Ni 2+ release. In addition, the Ni 2+ release amount increases with nanopore length. The anodized samples show good cytocompatibility when the nanopore length is <11 μm. Encouragingly, the length scale covers the one (1-11 μm) that the nanopores showing favorable antibacterial ability. Consequently, the nanopores with length in the range of 1-11 μm are promising as coatings of biomedical NiTi alloy for anti-infection, drug delivery, and other desirable applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality.

PubMed

Fujita, Takeshi

2017-01-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Noise Properties of Rectifying Nanopore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vlassiouk, Ivan V

2011-01-01

Ion currents through three types of rectifying nanoporous structures are studied and compared: conically shaped polymer nanopores, glass nanopipettes, and silicon nitride nanopores. Time signals of ion currents are analyzed by the power spectrum. We focus on the low-frequency range where the power spectrum magnitude scales with frequency, f, as 1/f. Glass nanopipettes and polymer nanopores exhibit nonequilibrium 1/f noise; thus, the normalized power spectrum depends on the voltage polarity and magnitude. In contrast, 1/f noise in rectifying silicon nitride nanopores is of equilibrium character. Various mechanisms underlying the voltage-dependent 1/f noise are explored and discussed, including intrinsic pore wallmore » dynamics and formation of vortices and nonlinear flow patterns in the pore. Experimental data are supported by modeling of ion currents based on the coupled Poisson-Nernst-Planck and Navier-Stokes equations. We conclude that the voltage-dependent 1/f noise observed in polymer and glass asymmetric nanopores might result from high and asymmetric electric fields, inducing secondary effects in the pore, such as enhanced water dissociation.« less

Mechanism of How Salt-Gradient-Induced Charges Affect the Translocation of DNA Molecules through a Nanopore

PubMed Central

He, Yuhui; Tsutsui, Makusu; Scheicher, Ralph H.; Fan, Chun; Taniguchi, Masateru; Kawai, Tomoji

2013-01-01

Experiments using nanopores demonstrated that a salt gradient enhances the capture rate of DNA and reduces its translocation speed. These two effects can help to enable electrical DNA sequencing with nanopores. Here, we provide a quantitative theoretical evaluation that shows the positive net charges, which accumulate around the pore entrance due to the salt gradient, are responsible for the two observed effects: they reinforce the electric capture field, resulting in promoted molecule capture rate; and they induce cationic electroosmotic flow through the nanopore, thus significantly retarding the motion of the anionic DNA through the nanopore. Our multiphysical simulation results show that, during the polymer trapping stage, the former effect plays the major role, thus resulting in promoted DNA capture rate, while during the nanopore-penetrating stage the latter effect dominates and consequently reduces the DNA translocation speed significantly. Quantitative agreement with experimental results has been reached by further taking nanopore wall surface charges into account. PMID:23931325

One-step synthesis of zero-dimensional hollow nanoporous gold nanoparticles with enhanced methanol electrooxidation performance.

PubMed

Pedireddy, Srikanth; Lee, Hiang Kwee; Tjiu, Weng Weei; Phang, In Yee; Tan, Hui Ru; Chua, Shu Quan; Troadec, Cedric; Ling, Xing Yi

2014-09-17

Nanoporous gold with networks of interconnected ligaments and highly porous structure holds stimulating technological implications in fuel cell catalysis. Current syntheses of nanoporous gold mainly revolve around de-alloying approaches that are generally limited by stringent and harsh multistep protocols. Here we develop a one-step solution phase synthesis of zero-dimensional hollow nanoporous gold nanoparticles with tunable particle size (150-1,000 nm) and ligament thickness (21-54 nm). With faster mass diffusivity, excellent specific electroactive surface area and large density of highly active surface sites, our zero-dimensional nanoporous gold nanoparticles exhibit ~1.4 times enhanced catalytic activity and improved tolerance towards carbonaceous species, demonstrating their superiority over conventional nanoporous gold sheets. Detailed mechanistic study also reveals the crucial heteroepitaxial growth of gold on the surface of silver chloride templates, implying that our synthetic protocol is generic and may be extended to the synthesis of other nanoporous metals via different templates.

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

PubMed Central

Fujita, Takeshi

2017-01-01

Abstract Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals. PMID:29057026

Theoretical and experimental studies on ionic currents in nanopore-based biosensors.

PubMed

Liu, Lei; Li, Chu; Ma, Jian; Wu, Yingdong; Ni, Zhonghua; Chen, Yunfei

2014-12-01

Novel generation of analytical technology based on nanopores has provided possibilities to fabricate nanofluidic devices for low-cost DNA sequencing or rapid biosensing. In this paper, a simplified model was suggested to describe DNA molecule's translocation through a nanopore, and the internal potential, ion concentration, ionic flowing speed and ionic current in nanopores with different sizes were theoretically calculated and discussed on the basis of Poisson-Boltzmann equation, Navier-Stokes equation and Nernst-Planck equation by considering several important parameters, such as the applied voltage, the thickness and the electric potential distributions in nanopores. In this way, the basic ionic currents, the modulated ionic currents and the current drops induced by translocation were obtained, and the size effects of the nanopores were carefully compared and discussed based on the calculated results and experimental data, which indicated that nanopores with a size of 10 nm or so are more advantageous to achieve high quality ionic current signals in DNA sensing.

Tailored nanoporous coatings fabricated on conformable polymer substrates.

PubMed

Poxson, David J; Mont, Frank W; Cho, Jaehee; Schubert, E Fred; Siegel, Richard W

2012-11-01

Nanoporous coatings have become the subject of intense investigation, in part because they have been shown to have unique and tailorable physical properties that can depart greatly from their dense or macroscopic counterparts. Nanoporous coatings are frequently fabricated utilizing oblique-angle or glancing-angle physical vapor-phase deposition techniques. However, a significant limitation for such coatings exists; they are almost always deposited on smooth and rigid planar substrates, such as silicon and glass. This limitation greatly constrains the applicability, tailorability, functionality and even the economic viability, of such nanoporous coatings. Here, we report our findings on nanoporous/polymer composite systems (NPCS) fabricated by utilizing oblique-angle electron-beam methodology. These unique composite systems exhibit several favorable characteristics, namely, (i) fine-tuned control over coating nanoporosity and thickness, (ii) excellent adhesion between the nanoporous coating and polymer substrate, (iii) the ability to withstand significant and repeated bending, and (iv) the ability to be molded conformably on two and three-dimensional surfaces while closely retaining the composite system's designed nanoporous film structure and, hence, properties.

DNA Origami-Graphene Hybrid Nanopore for DNA Detection.

PubMed

Barati Farimani, Amir; Dibaeinia, Payam; Aluru, Narayana R

2017-01-11

DNA origami nanostructures can be used to functionalize solid-state nanopores for single molecule studies. In this study, we characterized a nanopore in a DNA origami-graphene heterostructure for DNA detection. The DNA origami nanopore is functionalized with a specific nucleotide type at the edge of the pore. Using extensive molecular dynamics (MD) simulations, we computed and analyzed the ionic conductivity of nanopores in heterostructures carpeted with one or two layers of DNA origami on graphene. We demonstrate that a nanopore in DNA origami-graphene gives rise to distinguishable dwell times for the four DNA base types, whereas for a nanopore in bare graphene, the dwell time is almost the same for all types of bases. The specific interactions (hydrogen bonds) between DNA origami and the translocating DNA strand yield different residence times and ionic currents. We also conclude that the speed of DNA translocation decreases due to the friction between the dangling bases at the pore mouth and the sequencing DNA strands.

Impedance nanopore biosensor: influence of pore dimensions on biosensing performance.

PubMed

Kant, Krishna; Yu, Jingxian; Priest, Craig; Shapter, Joe G; Losic, Dusan

2014-03-07

Knowledge about electrochemical and electrical properties of nanopore structures and the influence of pore dimensions on these properties is important for the development of nanopore biosensing devices. The aim of this study was to explore the influence of nanopore dimensions (diameter and length) on biosensing performance using non-faradic electrochemical impedance spectroscopy (EIS). Nanoporous alumina membranes (NPAMs) prepared by self-ordered electrochemical anodization of aluminium were used as model nanopore sensing platforms. NPAMs with different pore diameters (25-65 nm) and lengths (4-18 μm) were prepared and the internal pore surface chemistry was modified by covalently attaching streptavidin and biotin. The performance of this antibody nanopore biosensing platform was evaluated using various concentrations of biotin as a model analyte. EIS measurements of pore resistivity and conductivity were carried out for pores with different diameters and lengths. The results showed that smaller pore dimensions of 25 nm and pore lengths up to 10 μm provide better biosensing performance.

The Influence of Nanopore Dimensions on the Electrochemical Properties of Nanopore Arrays Studied by Impedance Spectroscopy

PubMed Central

Kant, Krishna; Priest, Craig; Shapter, Joe G.; Losic, Dusan

2014-01-01

The understanding of the electrochemical properties of nanopores is the key factor for better understanding their performance and applications for nanopore-based sensing devices. In this study, the influence of pore dimensions of nanoporous alumina (NPA) membranes prepared by an anodization process and their electrochemical properties as a sensing platform using impedance spectroscopy was explored. NPA with four different pore diameters (25 nm, 45 nm and 65 nm) and lengths (5 μm to 20 μm) was used and their electrochemical properties were explored using different concentration of electrolyte solution (NaCl) ranging from 1 to 100 μM. Our results show that the impedance and resistance of nanopores are influenced by the concentration and ion species of electrolytes, while the capacitance is independent of them. It was found that nanopore diameters also have a significant influence on impedance due to changes in the thickness of the double layer inside the pores. PMID:25393785

One-step synthesis of zero-dimensional hollow nanoporous gold nanoparticles with enhanced methanol electrooxidation performance

NASA Astrophysics Data System (ADS)

Pedireddy, Srikanth; Lee, Hiang Kwee; Tjiu, Weng Weei; Phang, In Yee; Tan, Hui Ru; Chua, Shu Quan; Troadec, Cedric; Ling, Xing Yi

2014-09-01

Nanoporous gold with networks of interconnected ligaments and highly porous structure holds stimulating technological implications in fuel cell catalysis. Current syntheses of nanoporous gold mainly revolve around de-alloying approaches that are generally limited by stringent and harsh multistep protocols. Here we develop a one-step solution phase synthesis of zero-dimensional hollow nanoporous gold nanoparticles with tunable particle size (150-1,000 nm) and ligament thickness (21-54 nm). With faster mass diffusivity, excellent specific electroactive surface area and large density of highly active surface sites, our zero-dimensional nanoporous gold nanoparticles exhibit ~1.4 times enhanced catalytic activity and improved tolerance towards carbonaceous species, demonstrating their superiority over conventional nanoporous gold sheets. Detailed mechanistic study also reveals the crucial heteroepitaxial growth of gold on the surface of silver chloride templates, implying that our synthetic protocol is generic and may be extended to the synthesis of other nanoporous metals via different templates.

Nanoporous Ag prepared from the melt-spun Cu-Ag alloys

NASA Astrophysics Data System (ADS)

Li, Guijing; Song, Xiaoping; Sun, Zhanbo; Yang, Shengchun; Ding, Bingjun; Yang, Sen; Yang, Zhimao; Wang, Fei

2011-07-01

Nanoporous Ag ribbons with different morphology and porosity were achieved by the electrochemical corrosion of the melt-spun Cu-Ag alloys. The Cu-rich phase in the alloys was removed, resulting in the formation of the nanopores distributed across the whole ribbon. It is found that the structures, morphology and porosity of the nanoporous Ag ribbons were dependent on the microstructures of the parent alloys. The most of ligaments presented a rod-like shape due to the formation of pseudoeutectic microstructure in the melt-spun Cu 55Ag 45 and Cu 70Ag 30 alloys. For nanoporous Ag prepared from Cu 85Ag 15 alloys, the ligaments were camber-like because of the appearance of the divorced microstructures. Especially, a novel bamboo-grove-like structure could be observed at the cross-section of the nanoporous Ag ribbons. The experiment reveals that nanoporous Ag ribbons exhibited excellent enhancement of surface-enhanced Raman scattering (SERS) effect, but a slight difference existed due to the discrepancy of their morphology.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Hierarchical nanoporous metals as a path toward the ultimate three-dimensional functionality

NASA Astrophysics Data System (ADS)

Fujita, Takeshi

2017-12-01

Nanoporous metals prepared via dealloying or selective leaching of solid solution alloys and compounds represent an emerging class of materials. They possess a three-dimensional (3D) structure of randomly interpenetrating ligaments/nanopores with sizes between 5 nm and several tens of micrometers, which can be tuned by varying their preparation conditions (such as dealloying time and temperature) or additional thermal coarsening. As compared to other nanostructured materials, nanoporous metals have many advantages, including their bicontinuous structure, tunable pore sizes, bulk form, good electrical conductivity, and high structural stability. Therefore, nanoporous metals represent ideal 3D materials with versatile functionality, which can be utilized in various fields. In this review, we describe the recent applications of nanoporous metals in molecular detection, catalysis, 3D graphene synthesis, hierarchical pore formation, and additive manufacturing (3D printing) together with our own achievements in these areas. Finally, we discuss possible ways of realizing the ultimate 3D functionality beyond the scope of nanoporous metals.

Lithography-based fabrication of nanopore arrays in freestanding SiN and graphene membranes

NASA Astrophysics Data System (ADS)

Verschueren, Daniel V.; Yang, Wayne; Dekker, Cees

2018-04-01

We report a simple and scalable technique for the fabrication of nanopore arrays on freestanding SiN and graphene membranes based on electron-beam lithography and reactive ion etching. By controlling the dose of the single-shot electron-beam exposure, circular nanopores of any size down to 16 nm in diameter can be fabricated in both materials at high accuracy and precision. We demonstrate the sensing capabilities of these nanopores by translocating dsDNA through pores fabricated using this method, and find signal-to-noise characteristics on par with transmission-electron-microscope-drilled nanopores. This versatile lithography-based approach allows for the high-throughput manufacturing of nanopores and can in principle be used on any substrate, in particular membranes made out of transferable two-dimensional materials.

Graphene nanopore devices for DNA sensing.

PubMed

Merchant, Chris A; Drndić, Marija

2012-01-01

We describe here a method for detecting the translocation of individual DNA molecules through nanopores created in graphene membranes. The devices consist of 1-5-nm thick graphene membranes with electron-beam sculpted nanopores from 5 to 10 nm in diameter. Due to the thin nature of the graphene membranes, and the reduced electrical resistance, we observe larger blocked currents than for traditional solid-state nanopores. We also show how ionic current noise levels can be reduced with the atomic-layer deposition of a few nanometers of titanium dioxide over the graphene surface. Unlike traditional solid-state nanopore materials that are insulating, graphene is an excellent electrical conductor, and its use opens the door to a new future class of nanopore devices in which electronic sensing and control is performed directly at the pore.

The Utility of Nanopore Technology for Protein and Peptide Sensing.

PubMed

Robertson, Joseph W F; Reiner, Joseph E

2018-06-28

Resistive-pulse nanopore sensing enables label-free single-molecule analysis of a wide range of analytes. An increasing number of studies have demonstrated the feasibility and usefulness of nanopore sensing for protein and peptide characterization. Nanopores offer the potential to study a variety of protein-related phenomena that includes unfolding kinetics, differences in unfolding pathways, protein structure stability and free energy profiles of DNA-protein and RNA-protein binding. In addition to providing a tool for fundamental protein characterization, nanopores have also been used as highly selective protein detectors in various solution mixtures and conditions. This review highlights these and other developments in the area of nanopore-based protein and peptide detection. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Single Nanopore Investigations with Ion Conductance Microscopy

PubMed Central

Chen, Chiao-Chen; Zhou, Yi; Baker, Lane A.

2011-01-01

A three-electrode scanning ion conductance microscope (SICM) was used to investigate the local current-voltage properties of a single nanopore. In this experimental configuration, the response measured is a function of changes in the resistances involved in the pathways of ion migration. Single nanopore membranes utilized in this study were prepared with an epoxy painting procedure to isolate a single nanopore from a track-etch multi-pore membrane. Current-voltage responses measured with the SICM probe in the vicinity of a single nanopore were investigated in detail and agreed well with equivalent circuit models proposed in this study. With this modified SICM, the current-voltage responses characterized for the case of a single cylindrical pore and a single conical pore exhibit distinct conductance properties that originate from the geometry of nanopores. PMID:21923184

Biological Nanopores: Confined Spaces for Electrochemical Single-Molecule Analysis.

PubMed

Cao, Chan; Long, Yi-Tao

2018-02-20

Nanopore sensing is developing into a powerful single-molecule approach to investigate the features of biomolecules that are not accessible by studying ensemble systems. When a target molecule is transported through a nanopore, the ions occupying the pore are excluded, resulting in an electrical signal from the intermittent ionic blockade event. By statistical analysis of the amplitudes, duration, frequencies, and shapes of the blockade events, many properties of the target molecule can be obtained in real time at the single-molecule level, including its size, conformation, structure, charge, geometry, and interactions with other molecules. With the development of the use of α-hemolysin to characterize individual polynucleotides, nanopore technology has attracted a wide range of research interest in the fields of biology, physics, chemistry, and nanoscience. As a powerful single-molecule analytical method, nanopore technology has been applied for the detection of various biomolecules, including oligonucleotides, peptides, oligosaccharides, organic molecules, and disease-related proteins. In this Account, we highlight recent developments of biological nanopores in DNA-based sensing and in studying the conformational structures of DNA and RNA. Furthermore, we introduce the application of biological nanopores to investigate the conformations of peptides affected by charge, length, and dipole moment and to study disease-related proteins' structures and aggregation transitions influenced by an inhibitor, a promoter, or an applied voltage. To improve the sensing ability of biological nanopores and further extend their application to a wider range of molecular sensing, we focus on exploring novel biological nanopores, such as aerolysin and Stable Protein 1. Aerolysin exhibits an especially high sensitivity for the detection of single oligonucleotides both in current separation and duration. Finally, to facilitate the use of nanopore measurements and statistical analysis, we develop an integrated current measurement system and an accurate data processing method for nanopore sensing. The unique geometric structure of a biological nanopore offers a distinct advantage as a nanosensor for single-molecule sensing. The construction of the pore entrance is responsible for capturing the target molecule, while the lumen region determines the translocation process of the single molecule. Since the capture of the target molecule is predominantly diffusion-limited, it is expected that the capture ability of the nanopore toward the target analyte could be effectively enhanced by site-directed mutations of key amino acids with desirable groups. Additionally, changing the side chains inside the wall of the biological nanopore could optimize the geometry of the pore and realize an optimal interaction between the single-molecule interface and the analyte. These improvements would allow for high spatial and current resolution of nanopore sensors, which would ensure the possibility of dynamic study of single biomolecules, including their metastable conformations, charge distributions, and interactions. In the future, data analysis with powerful algorithms will make it possible to automatically and statistically extract detailed information while an analyte translocates through the pore. We conclude that these improvements could have tremendous potential applications for nanopore sensing in the near future.

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

2013-03-12

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

2010-12-07

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Study of polymer molecules and conformations with a nanopore

DOEpatents

Golovchenko, Jene A; Li, Jiali; Stein, Derek; Gershow, Marc H

2015-03-03

The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

Integration of solid-state nanopores in a 0.5 μm cmos foundry process

PubMed Central

Uddin, A; Yemenicioglu, S; Chen, C-H; Corigliano, E; Milaninia, K; Theogarajan, L

2013-01-01

High-bandwidth and low-noise nanopore sensor and detection electronics are crucial in achieving single-DNA base resolution. A potential way to accomplish this goal is to integrate solid-state nanopores within a CMOS platform, in close proximity to the biasing electrodes and custom-designed amplifier electronics. Here we report the integration of solid-state nanopore devices in a commercial complementary metal-oxide semiconductor (CMOS) potentiostat chip implemented in On-Semiconductor’s 0.5 μm technology. Nanopore membranes incorporating electrodes are fabricated by post-CMOS micromachining utilizing the N+ polysilicon/SiO2/N+ polysilicon capacitor structure available in the aforementioned process. Nanopores are created in the CMOS process by drilling in a transmission electron microscope and shrinking by atomic layer deposition. We also describe a batch fabrication method to process a large of number of electrode-embedded nanopores with sub-10 nm diameter across CMOS-compatible wafers by electron beam lithography and atomic layer deposition. The CMOS-compatibility of our fabrication process is verified by testing the electrical functionality of on-chip circuitry. We observe high current leakage with the CMOS nanopore devices due to the ionic diffusion through the SiO2 membrane. To prevent this leakage, we coat the membrane with Al2O3 which acts as an efficient diffusion barrier against alkali ions. The resulting nanopore devices also exhibit higher robustness and lower 1/f noise as compared to SiO2 and SiNx. Furthermore, we propose a theoretical model for our low-capacitance CMOS nanopore devices, showing good agreement with the experimental value. In addition, experiments and theoretical models of translocation studies are presented using 48.5 kbp λ-DNA in order to prove the functionality of on-chip pores coated with Al2O3. PMID:23519330

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays.

PubMed

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm(-2), which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

In vitro extracellular recording and stimulation performance of nanoporous gold-modified multi-electrode arrays

NASA Astrophysics Data System (ADS)

Kim, Yong Hee; Kim, Gook Hwa; Kim, Ah Young; Han, Young Hwan; Chung, Myung-Ae; Jung, Sang-Don

2015-12-01

Objective. Nanoporous gold (Au) structures can reduce the impedance and enhance the charge injection capability of multi-electrode arrays (MEAs) used for interfacing neuronal networks. Even though there are various nanoporous Au preparation techniques, fabrication of MEA based on low-cost electro-codeposition of Ag:Au has not been performed. In this work, we have modified a Au MEA via the electro-codeposition of Ag:Au alloy, followed by the chemical etching of Ag, and report on the in vitro extracellular recording and stimulation performance of the nanoporous Au-modified MEA. Approach. Ag:Au alloy was electro-codeposited on a bilayer lift-off resist sputter-deposition passivated Au MEA followed by chemical etching of Ag to form a porous Au structure. Main results. The porous Au structure was analyzed by scanning electron microscopy and tunneling electron microscopy and found to have an interconnected nanoporous Au structure. The impedance value of the nanoporous Au-modified MEA is 15.4 ± 0.55 kΩ at 1 kHz, accompanied by the base noise V rms of 2.4 ± 0.3 μV. The charge injection limit of the nanoporous Au-modified electrode estimated from voltage transient measurement is approximately 1 mC cm-2, which is comparable to roughened platinum and carbon nanotube electrodes. The charge injection capability of the nanoporous Au-modified MEA was confirmed by observing stimulus-induced spikes at above 0.2 V. The nanoporous Au-modified MEA showed mechanical durability upon ultrasonic treatment for up to an hour. Significance. Electro-codeposition of Ag:Au alloy combined with chemical etching Ag is a low-cost process for fabricating nanoporous Au-modified MEA suitable for establishing the stimulus-response relationship of cultured neuronal networks.

Nanopore formation in neuroblastoma cells following ultrashort electric pulse exposure

NASA Astrophysics Data System (ADS)

Roth, Caleb C.; Payne, Jason A.; Wilmink, Gerald J.; Ibey, Bennett L.

2011-03-01

Ultrashort or nanosecond electrical pulses (USEP) cause repairable damage to the plasma membranes of cells through formation of nanopores. These nanopores are able to pass small ions such as sodium, calcium, and potassium, but remain impermeable to larger molecules like trypan blue and propidium iodide. What remains uncertain is whether generation of nanopores by ultrashort electrical pulses can inhibit action potentials in excitable cells. In this paper, we explored the sensitivity of excitable cells to USEP using Calcium Green AM 1 ester fluorescence to measure calcium uptake indicative of nanopore formation in the plasma membrane. We determined the threshold for nanopore formation in neuroblastoma cells for three pulse parameters (amplitude, pulse width, and pulse number). Measurement of such thresholds will guide future studies to determine if USEP can inhibit action potentials without causing irreversible membrane damage.

A novel input-parasitic compensation technique for a nanopore-based CMOS DNA detection sensor

NASA Astrophysics Data System (ADS)

Kim, Jungsuk

2016-12-01

This paper presents a novel input-parasitic compensation (IPC) technique for a nanopore-based complementary metal-oxide-semiconductor (CMOS) DNA detection sensor. A resistive-feedback transimpedance amplifier is typically adopted as the headstage of a DNA detection sensor to amplify the minute ionic currents generated from a nanopore and convert them to a readable voltage range for digitization. But, parasitic capacitances arising from the headstage input and the nanopore often cause headstage saturation during nanopore sensing, thereby resulting in significant DNA data loss. To compensate for the unwanted saturation, in this work, we propose an area-efficient and automated IPC technique, customized for a low-noise DNA detection sensor, fabricated using a 0.35- μm CMOS process; we demonstrated this prototype in a benchtop test using an α-hemolysin ( α-HL) protein nanopore.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Adiabatic burst evaporation from bicontinuous nanoporous membranes

PubMed Central

Ichilmann, Sachar; Rücker, Kerstin; Haase, Markus; Enke, Dirk

2015-01-01

Evaporation of volatile liquids from nanoporous media with bicontinuous morphology and pore diameters of a few 10 nm is an ubiquitous process. For example, such drying processes occur during syntheses of nanoporous materials by sol–gel chemistry or by spinodal decomposition in the presence of solvents as well as during solution impregnation of nanoporous hosts with functional guests. It is commonly assumed that drying is endothermic and driven by non-equilibrium partial pressures of the evaporating species in the gas phase. We show that nearly half of the liquid evaporates in an adiabatic mode involving burst-like liquid-to-gas conversions. During single adiabatic burst evaporation events liquid volumes of up to 107 μm3 are converted to gas. The adiabatic liquid-to-gas conversions occur if air invasion fronts get unstable because of the built-up of high capillary pressures. Adiabatic evaporation bursts propagate avalanche-like through the nanopore systems until the air invasion fronts have reached new stable configurations. Adiabatic cavitation bursts thus compete with Haines jumps involving air invasion front relaxation by local liquid flow without enhanced mass transport out of the nanoporous medium and prevail if the mean pore diameter is in the range of a few 10 nm. The results reported here may help optimize membrane preparation via solvent-based approaches, solution-loading of nanopore systems with guest materials as well as routine use of nanoporous membranes with bicontinuous morphology and may contribute to better understanding of adsorption/desorption processes in nanoporous media. PMID:25926406

Propylene/propane permeation properties of ethyl cellulose (EC) mixed matrix membranes fabricated by incorporation of nanoporous graphene nanosheets

PubMed Central

Yuan, Bingbing; Sun, Haixiang; Wang, Tao; Xu, Yanyan; Li, Peng; Kong, Ying; Niu, Q. Jason

2016-01-01

Nanopore containing graphene nanosheets were synthesized by graphene oxide and a reducing agent using a facile hydrothermal treatment in sodium hydroxide media. The as-prepared nanoporous graphene was incorporated into ethyl cellulose (EC) to prepare the mixed matrix membranes (MMMs) for C3H6/C3H8 separation. Transmission electron microscopy (TEM) photograph and X-ray photoelectron spectroscopy (XPS) analysis of nanoporous graphene nanosheets indicated that the structure of nano-pore was irregular and the oxygen-containing groups in the surface were limited. More importantly, the as-prepared MMMs presented better separation performance than that of pristine EC membrane due to simultaneous enhancement of C3H6 permeability and ideal selectivity. The ideal selectivity of the MMMs with 1.125 wt‰ nanoporous graphene content for C3H6/C3H8 increased from 3.45 to 10.42 and the permeability of C3H6 increased from 57.9 Barrer to 89.95 Barrer as compared with the pristine membrane. The presumed facilitated mechanism was that the high specific surface area of nanoporous graphene in polymer matrix increased the length of the tortuous pathway formed by nanopores for the gas diffusion as compared with the pristine graphene nanosheets, and generated a rigidified interface between the EC chains and fillers, thus enhanced the diffusivity selectivity. Therefore, it is expected that nanoporous graphene would be effective material for the C3H6/C3H8 separation. PMID:27352851

Nanoporous Au: An experimental study on the porosity of dealloyed AuAg leafs

NASA Astrophysics Data System (ADS)

Grillo, R.; Torrisi, V.; Ruffino, F.

2016-12-01

We present a study on the fraction of porosity for dealloyed nanoporous Au leafs. Nanoporous Au is attracting great scientific interest due to its peculiar plasmonic properties and the high exposed surface (∼10 m2/g). As examples, it was used in prototypes of chemical and biological devices. However, the maximization of the devices sensitivity is subjected to the maximization of the exposed surface by the nanoporous Au, i. e. maximization of the porosity fraction. So, we report on the analyses of the porosity fraction in nanoporous Au leafs as a function of the fabrication process parameters. We dealloyed 60 μm-thick Au23Ag77 at.% leafs and we show that: a) for dealloying time till to 6 h, only a 450 nm-thick surface layer of the leafs assumes a nanoporous structure with a porosity fraction of 32%. For a dealloying time of 20 h the leafs result fragmented in small black pieces with a porosity fraction increased to 60%. b) After 600 °C-30 minutes annealing of the previous samples, the nanopores disappear due to the Au/residual Ag inter-diffusion. c) After a second dealloying process on the previously annealed samples, the surface nanoporous structure is, again, obtained with the porosity fraction increased to 50%.

Amphotericin B channels in phospholipid membrane-coated nanoporous silicon surfaces: implications for photovoltaic driving of ions across membranes.

PubMed

Yilma, Solomon; Liu, Nangou; Samoylov, Alexander; Lo, Ting; Brinker, C Jeffrey; Vodyanoy, Vitaly

2007-03-15

The antimycotic agent amphotericin B (AmB) functions by forming complexes with sterols to form ion channels that cause membrane leakage. When AmB and cholesterol mixed at 2:1 ratio were incorporated into phospholipid bilayer membranes formed on the tip of patch pipettes, ion channel current fluctuations with characteristic open and closed states were observed. These channels were also functional in phospholipid membranes formed on nanoporous silicon surfaces. Electrophysiological studies of AmB-cholesterol mixtures that were incorporated into phospholipid membranes formed on the surface of nanoporous (6.5 nm pore diameter) silicon plates revealed large conductance ion channels ( approximately 300 pS) with distinct open and closed states. Currents through the AmB-cholesterol channels on nanoporous silicon surfaces can be driven by voltage applied via conventional electrical circuits or by photovoltaic electrical potential entirely generated when the nanoporous silicon surface is illuminated with a narrow laser beam. Electrical recordings made during laser illumination of AmB-cholesterol containing membrane-coated nanoporous silicon surfaces revealed very large conductance ion channels with distinct open and closed states. Our findings indicate that nanoporous silicon surfaces can serve as mediums for ion-channel-based biosensors. The photovoltaic properties of nanoporous silicon surfaces show great promise for making such biosensors addressable via optical technologies.

Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: a tool for investigating the role of the polymer host.

PubMed

Buonerba, Antonio; Noschese, Annarita; Grassi, Alfonso

2014-04-25

The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4-polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea = 57.8±11.5 and 62.7±16.7 kJ mol(-1) for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafine nanoporous palladium-aluminum film fabricated by citric acid-assisted hot-water-treatment of aluminum-palladium alloy film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harumoto, Takashi; Tamura, Yohei; Ishiguro, Takashi, E-mail: ishiguro@rs.noda.tus.ac.jp

Hot-water-treatment has been adapted to fabricate ultrafine nanoporous palladium-aluminum film from aluminum-palladium alloy film. Using citric acid as a chelating agent, a precipitation of boehmite (aluminum oxide hydroxide, AlOOH) on the nanoporous palladium-aluminum film was suppressed. According to cross-sectional scanning transmission electron microscopy observations, the ligament/pore sizes of the prepared nanoporous film were considerably small (on the order of 10 nm). Since this fabrication method only requires aluminum alloy film and hot-water with chelating agent, the ultrafine nanoporous film can be prepared simply and environmentally friendly.

Thermoelectric studies of nanoporous thin films with adjusted pore-edge charges

NASA Astrophysics Data System (ADS)

Hao, Qing; Zhao, Hongbo; Xu, Dongchao

2017-03-01

In recent years, nanoporous thin films have been widely studied for thermoelectric applications. High thermoelectric performance is reported for nanoporous Si films, which is attributed to the dramatically reduced lattice thermal conductivity and bulk-like electrical properties. Porous materials can also be used in gas sensing applications by engineering the surface-trapped charges on pore edges. In this work, an analytical model is developed to explore the relationship between the thermoelectric properties and pore-edge charges in a periodic two-dimensional nanoporous material. The presented model can be widely used to analyze the measured electrical properties of general nanoporous thin films and two-dimensional materials.

Noise Properties of Rectifying Nanopores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, M R; Sa, N; Davenport, M

2011-02-18

Ion currents through three types of rectifying nanoporous structures are studied and compared for the first time: conically shaped polymer nanopores, glass nanopipettes, and silicon nitride nanopores. Time signals of ion currents are analyzed by power spectrum. We focus on the low-frequency range where the power spectrum magnitude scales with frequency, f, as 1/f. Glass nanopipettes and polymer nanopores exhibit non-equilibrium 1/f noise, thus the normalized power spectrum depends on the voltage polarity and magnitude. In contrast, 1/f noise in rectifying silicon nitride nanopores is of equilibrium character. Various mechanisms underlying the voltage-dependent 1/f noise are explored and discussed, includingmore » intrinsic pore wall dynamics, and formation of vortices and non-linear flow patterns in the pore. Experimental data are supported by modeling of ion currents based on the coupled Poisson-Nernst-Planck and Navier Stokes equations. We conclude that the voltage-dependent 1/f noise observed in polymer and glass asymmetric nanopores might result from high and asymmetric electric fields inducing secondary effects in the pore such as enhanced water dissociation.« less

Surface effects on ionic Coulomb blockade in nanometer-size pores

NASA Astrophysics Data System (ADS)

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V.; Di Ventra, Massimiliano

2018-01-01

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying ‘crystal-like’ structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Surface effects on ionic Coulomb blockade in nanometer-size pores.

PubMed

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V; Ventra, Massimiliano Di

2018-01-12

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying 'crystal-like' structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Synthetic Nanopores as a Test Case for Ion Channel Theories: The Anomalous Mole Fraction Effect without Single Filing

PubMed Central

Gillespie, Dirk; Boda, Dezső; He, Yan; Apel, Pavel; Siwy, Zuzanna S.

2008-01-01

The predictions of a theory for the anomalous mole fraction effect (AMFE) are tested experimentally with synthetic nanopores in plastic. The negatively charged synthetic nanopores under consideration are highly cation selective and 50 Å in diameter at their smallest point. These pores exhibit an AMFE in mixtures of Ca2+ and monovalent cations. An AMFE occurs when the conductance through a pore is lower in a mixture of salts than in the pure salts at the same concentration. For ion channels, the textbook interpretation of the AMFE is that multiple ions move through the pore in coordinated, single-file motion. However, because the synthetic nanopores are so wide, their AMFE shows that single filing is not necessary for the AMFE. It is shown that the AMFE in the synthetic nanopores is explained by a theory of preferential ion selectivity. The unique properties of the synthetic nanopores allow us to experimentally confirm several predictions of this theory. These same properties make synthetic nanopores an interesting new platform to test theories of ion channel permeation and selectivity in general. PMID:18390596

Biomimetic glass nanopores employing aptamer gates responsive to a small molecule†

PubMed Central

Abelow, Alexis E.; Schepelina, Olga; White, Ryan J.; Vallée-Bélisle, Alexis

2011-01-01

We report the preparation of 20 and 65 nm radii glass nanopores whose surface is modified with DNA aptamers controlling the molecular transport through the nanopores in response to small molecule binding. PMID:20865192

Anti-reflective nanoporous silicon for efficient hydrogen production

DOEpatents

Oh, Jihun; Branz, Howard M

2014-05-20

Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H.sub.2 production from water splitting half-reaction.

Applications of Nanoporous Materials in Agriculture

USDA-ARS?s Scientific Manuscript database

Nanoporous materials possess organized pore distributions and increased surface areas. Advances in the systematic design of nanoporous materials enable incorporation of functionality for better sensitivity in detection methods, increased capacity of sorbents, and improved selectivity and yield in ca...

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Ni with High Surface Area for Potential Hydrogen Storage Application.

PubMed

Zhou, Xiaocao; Zhao, Haibo; Fu, Zhibing; Qu, Jing; Zhong, Minglong; Yang, Xi; Yi, Yong; Wang, Chaoyang

2018-06-01

Nanoporous metals with considerable specific surface areas and hierarchical pore structures exhibit promising applications in the field of hydrogen storage, electrocatalysis, and fuel cells. In this manuscript, a facile method is demonstrated for fabricating nanoporous Ni with a high surface area by using SiO₂ aerogel as a template, i.e., electroless plating of Ni into an SiO₂ aerogel template followed by removal of the template at moderate conditions. The effects of the prepared conditions, including the electroless plating time, temperature of the structure, and the magnetism of nanoporous Ni are investigated in detail. The resultant optimum nanoporous Ni with a special 3D flower-like structure exhibited a high specific surface area of about 120.5 m²/g. The special nanoporous Ni exhibited a promising prospect in the field of hydrogen storage, with a hydrogen capacity of 0.45 wt % on 4.5 MPa at room temperature.

A Protein Nanopore-Based Approach for Bacteria Sensing

NASA Astrophysics Data System (ADS)

Apetrei, Aurelia; Ciuca, Andrei; Lee, Jong-kook; Seo, Chang Ho; Park, Yoonkyung; Luchian, Tudor

2016-11-01

We present herein a first proof of concept demonstrating the potential of a protein nanopore-based technique for real-time detection of selected Gram-negative bacteria ( Pseudomonas aeruginosa or Escherichia coli) at a concentration of 1.2 × 108 cfu/mL. The anionic charge on the bacterial outer membrane promotes the electrophoretically driven migration of bacteria towards a single α-hemolysin nanopore isolated in a lipid bilayer, clamped at a negative electric potential, and followed by capture at the nanopore's mouth, which we found to be described according to the classical Kramers' theory. By using a specific antimicrobial peptide as a putative molecular biorecognition element for the bacteria used herein, we suggest that the detection system can combine the natural sensitivity of the nanopore-based sensing techniques with selective biological recognition, in aqueous samples, and highlight the feasibility of the nanopore-based platform to provide portable, sensitive analysis and monitoring of bacterial pathogens.

Characterization of Nanoporous Materials with Atom Probe Tomography.

PubMed

Pfeiffer, Björn; Erichsen, Torben; Epler, Eike; Volkert, Cynthia A; Trompenaars, Piet; Nowak, Carsten

2015-06-01

A method to characterize open-cell nanoporous materials with atom probe tomography (APT) has been developed. For this, open-cell nanoporous gold with pore diameters of around 50 nm was used as a model system, and filled by electron beam-induced deposition (EBID) to obtain a compact material. Two different EBID precursors were successfully tested-dicobalt octacarbonyl [Co2(CO)8] and diiron nonacarbonyl [Fe2(CO)9]. Penetration and filling depth are sufficient for focused ion beam-based APT sample preparation. With this approach, stable APT analysis of the nanoporous material can be performed. Reconstruction reveals the composition of the deposited precursor and the nanoporous material, as well as chemical information of the interfaces between them. Thus, it is shown that, using an appropriate EBID process, local chemical information in three dimensions with sub-nanometer resolution can be obtained from nanoporous materials using APT.

Atomic layer deposition of TIO{sub 2} thin films on nanoporous alumina templates : medical applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narayan, R. J.; Monteiro-Riviere, N. A.; Brigmon, R. L.

2009-06-01

Nanostructured materials may play a significant role in controlled release of pharmacologic agents for treatment of cancer. Many nanoporous polymer materials are inadequate for use in drug delivery. Nanoporous alumina provides several advantages over other materials for use in controlled drug delivery and other medical applications. Atomic layer deposition was used to coat all the surfaces of a nanoporous alumina membrane in order to reduce the pore size in a controlled manner. Neither the 20 nm nor the 100 nm TiO{sub 2}-coated nanoporous alumina membranes exhibited statistically lower viability compared to the uncoated nanoporous alumina membrane control materials. Nanostructured materialsmore » prepared using atomic layer deposition may be useful for delivering a pharmacologic agent at a precise rate to a specific location in the body. These materials may serve as the basis for 'smart' drug delivery devices, orthopedic implants, or self-sterilizing medical devices.« less

Balancing size exclusion and adsorption of polymers in nanopores

NASA Astrophysics Data System (ADS)

Kim, Won; Ryu, Chang Y.

2006-03-01

The liquid chromatography at critical condition (LCCC) presents the condition, at which the size exclusion and adsorption of polymer chains are balanced upon interactions with nanoporous substrates. In this study, we investigate how the polymer interactions with nanopores are affected by the solvent quality and nanopore size. Specifically, we measure the retention times of monodisperse polystyrenes in C18-bonded nanoporous silica column as a function of molecular weight, when a mixed solvent of methylene chloride and acetonitrile are used as elutent. C18-bonded silica particles with 70, 100, and 250 A pore size are used as a stationary phase to study how the transition from SEC-like to IC-like retention behavior depends on the condition of temperature and solvent composition. To locate the LCCC at various nanopore sizes, the temperature and solvent composition have been varied from 0 to 60 C and from 51 to 62 v/v% of methylene chloride, respectively.

Pre-breakdown cavitation nanopores in the dielectric fluid in the inhomogeneous, pulsed electric fields

NASA Astrophysics Data System (ADS)

Pekker, Mikhail; Shneider, Mikhail N.

2015-10-01

This paper discusses the nanopores emerging and developing in a liquid dielectric under the action of the ponderomotive electrostrictive forces in a nonuniform electric field. It is shown that the gradient of the electric field in the vicinity of the rupture (cavitation nanopore) substantially increases and determines whether the rupture grows or collapses. The cavitation rupture in the liquid (nanopore) tends to stretch along the lines of the original field. The mechanism of the breakdown associated with the generation of secondary ruptures in the vicinity of the poles of the nanopore is proposed. The estimations of the extension time for nanopore in water and oil (polar and nonpolar liquids, respectively) are presented. A new mechanism of nano- and subnanosecond breakdown in the insulating (transformer) oil that can be realized in the vicinity of water microdroplets in nanosecond high-voltage devices is considered.

Tailoring the hydrophobicity of graphene for its use as nanopores for DNA translocation

NASA Astrophysics Data System (ADS)

Schneider, Grégory F.; Xu, Qiang; Hage, Susanne; Luik, Stephanie; Spoor, Johannes N. H.; Malladi, Sairam; Zandbergen, Henny; Dekker, Cees

2013-10-01

Graphene nanopores are potential successors to biological and silicon-based nanopores. For sensing applications, it is however crucial to understand and block the strong nonspecific hydrophobic interactions between DNA and graphene. Here we demonstrate a novel scheme to prevent DNA-graphene interactions, based on a tailored self-assembled monolayer. For bare graphene, we encounter a paradox: whereas contaminated graphene nanopores facilitated DNA translocation well, clean crystalline graphene pores very quickly exhibit clogging of the pore. We attribute this to strong interactions between DNA nucleotides and graphene, yielding sticking and irreversible pore closure. We develop a general strategy to noncovalently tailor the hydrophobic surface of graphene by designing a dedicated self-assembled monolayer of pyrene ethylene glycol, which renders the surface hydrophilic. We demonstrate that this prevents DNA to adsorb on graphene and show that single-stranded DNA can now be detected in graphene nanopores with excellent nanopore durability and reproducibility.

Molecular-based design and emerging applications of nanoporous carbon spheres

NASA Astrophysics Data System (ADS)

Liu, Jian; Wickramaratne, Nilantha P.; Qiao, Shi Zhang; Jaroniec, Mietek

2015-08-01

Over the past decade, considerable progress has been made in the synthesis and applications of nanoporous carbon spheres ranging in size from nanometres to micrometres. This Review presents the primary techniques for preparing nanoporous carbon spheres and the seminal research that has inspired their development, presented potential applications and uncovered future challenges. First we provide an overview of the synthesis techniques, including the Stöber method and those based on templating, self-assembly, emulsion and hydrothermal carbonization, with special emphasis on the design and functionalization of nanoporous carbon spheres at the molecular level. Next, we cover the key applications of these spheres, including adsorption, catalysis, separation, energy storage and biomedicine -- all of which might benefit from the regular geometry, good liquidity, tunable porosity and controllable particle-size distribution offered by nanoporous carbon spheres. Finally, we present the current challenges and opportunities in the development and commercial applications of nanoporous carbon spheres.

Molecular-based design and emerging applications of nanoporous carbon spheres.

PubMed

Liu, Jian; Wickramaratne, Nilantha P; Qiao, Shi Zhang; Jaroniec, Mietek

2015-08-01

Over the past decade, considerable progress has been made in the synthesis and applications of nanoporous carbon spheres ranging in size from nanometres to micrometres. This Review presents the primary techniques for preparing nanoporous carbon spheres and the seminal research that has inspired their development, presented potential applications and uncovered future challenges. First we provide an overview of the synthesis techniques, including the Stöber method and those based on templating, self-assembly, emulsion and hydrothermal carbonization, with special emphasis on the design and functionalization of nanoporous carbon spheres at the molecular level. Next, we cover the key applications of these spheres, including adsorption, catalysis, separation, energy storage and biomedicine — all of which might benefit from the regular geometry, good liquidity, tunable porosity and controllable particle-size distribution offered by nanoporous carbon spheres. Finally, we present the current challenges and opportunities in the development and commercial applications of nanoporous carbon spheres.

Transport of Proteins through Nanopores

NASA Astrophysics Data System (ADS)

Luan, Binquan

In biological cells, a malfunctioned protein (such as misfolded or damaged) is degraded by a protease in which an unfoldase actively drags the protein into a nanopore-like structure and then a peptidase cuts the linearized protein into small fragments (i.e. a recycling process). Mimicking this biological process, many experimental studies have focused on the transport of proteins through a biological protein pore or a synthetic solid-state nanopore. Potentially, the nanopore-based sensors can provide a platform for interrogating proteins that might be disease-related or be targeted by a new drug molecule. The single-profile of a protein chain inside an extremely small nanopore might even permit the sequencing of the protein. Here, through all-atom molecular dynamics simulations, I will show various types of protein transport through a nanopore and reveal the nanoscale mechanics/energetics that plays an important role governing the protein transport.

The role of nanopore shape in surface-induced crystallization

NASA Astrophysics Data System (ADS)

Diao, Ying; Harada, Takuya; Myerson, Allan S.; Alan Hatton, T.; Trout, Bernhardt L.

2011-11-01

Crystallization of a molecular liquid from solution often initiates at solid-liquid interfaces, and nucleation rates are generally believed to be enhanced by surface roughness. Here we show that, on a rough surface, the shape of surface nanopores can also alter nucleation kinetics. Using lithographic methods, we patterned polymer films with nanopores of various shapes and found that spherical nanopores 15-120 nm in diameter hindered nucleation of aspirin crystals, whereas angular nanopores of the same size promoted it. We also show that favourable surface-solute interactions are required for angular nanopores to promote nucleation, and propose that pore shape affects nucleation kinetics through the alteration of the orientational order of the crystallizing molecule near the angles of the pores. Our findings have clear technological implications, for instance in the control of pharmaceutical polymorphism and in the design of ‘seed’ particles for the regulation of crystallization of fine chemicals.

Voltage-Rectified Current and Fluid Flow in Conical Nanopores.

PubMed

Lan, Wen-Jie; Edwards, Martin A; Luo, Long; Perera, Rukshan T; Wu, Xiaojian; Martin, Charles R; White, Henry S

2016-11-15

Ion current rectification (ICR) refers to the asymmetric potential-dependent rate of the passage of solution ions through a nanopore, giving rise to electrical current-voltage characteristics that mimic those of a solid-state electrical diode. Since the discovery of ICR in quartz nanopipettes two decades ago, synthetic nanopores and nanochannels of various geometries, fabricated in membranes and on wafers, have been extensively investigated to understand fundamental aspects of ion transport in highly confined geometries. It is now generally accepted that ICR requires an asymmetric electrical double layer within the nanopore, producing an accumulation or depletion of charge-carrying ions at opposite voltage polarities. Our research groups have recently explored how the voltage-dependent ion distributions and ICR within nanopores can induce novel nanoscale flow phenomena that have applications in understanding ionics in porous materials used in energy storage devices, chemical sensing, and low-cost electrical pumping of fluids. In this Account, we review our most recent investigations on this topic, based on experiments using conical nanopores (10-300 nm tip opening) fabricated in thin glass, mica, and polymer membranes. Measurable fluid flow in nanopores can be induced either using external pressure forces, electrically via electroosmotic forces, or by a combination of these two forces. We demonstrate that pressure-driven flow can greatly alter the electrical properties of nanopores and, vice versa, that the nonlinear electrical properties of conical nanopores can impart novel and useful flow phenomena. Electroosmotic flow (EOF), which depends on the magnitude of the ion fluxes within the double layer of the nanopore, is strongly coupled to the accumulation/depletion of ions. Thus, the same underlying cause of ICR also leads to EOF rectification, i.e., unequal flows occurring for the same voltage but opposite polarities. EOF rectification can be used to electrically pump fluids with very precise control across membranes containing conical pores via the application of a symmetric sinusoidal voltage. The combination of pressure and asymmetric EOF can also provide a means to generate new nanopore electrical behaviors, including negative differential resistance (NDR), in which the current through a conical pore decreases with increasing driving force (applied voltage), similar to solid-state tunnel diodes. NDR results from a positive feedback mechanism between the ion distributions and EOF, yielding a true bistability in both fluid flow and electrical current at a critical applied voltage. Nanopore-based NDR is extremely sensitive to the surface charge near the nanopore opening, suggesting possible applications in chemical sensing.

Capture, Unfolding, and Detection of Individual tRNA Molecules Using a Nanopore Device

PubMed Central

Smith, Andrew M.; Abu-Shumays, Robin; Akeson, Mark; Bernick, David L.

2015-01-01

Transfer RNAs (tRNA) are the most common RNA molecules in cells and have critical roles as both translators of the genetic code and regulators of protein synthesis. As such, numerous methods have focused on studying tRNA abundance and regulation, with the most widely used methods being RNA-seq and microarrays. Though revolutionary to transcriptomics, these assays are limited by an inability to encode tRNA modifications in the requisite cDNA. These modifications are abundant in tRNA and critical to their function. Here, we describe proof-of-concept experiments where individual tRNA molecules are examined as linear strands using a biological nanopore. This method utilizes an enzymatically ligated synthetic DNA adapter to concentrate tRNA at the lipid bilayer of the nanopore device and efficiently denature individual tRNA molecules, as they are pulled through the α-hemolysin (α-HL) nanopore. Additionally, the DNA adapter provides a loading site for ϕ29 DNA polymerase (ϕ29 DNAP), which acts as a brake on the translocating tRNA. This increases the dwell time of adapted tRNA in the nanopore, allowing us to identify the region of the nanopore signal that is produced by the translocating tRNA itself. Using adapter-modified Escherichia coli tRNAfMet and tRNALys, we show that the nanopore signal during controlled translocation is dependent on the identity of the tRNA. This confirms that adapter-modified tRNA can translocate end-to-end through nanopores and provide the foundation for future work in direct sequencing of individual transfer RNA with a nanopore-based device. PMID:26157798

Real-time single-molecule electronic DNA sequencing by synthesis using polymer-tagged nucleotides on a nanopore array

PubMed Central

Fuller, Carl W.; Kumar, Shiv; Porel, Mintu; Chien, Minchen; Bibillo, Arek; Stranges, P. Benjamin; Dorwart, Michael; Tao, Chuanjuan; Li, Zengmin; Guo, Wenjing; Shi, Shundi; Korenblum, Daniel; Trans, Andrew; Aguirre, Anne; Liu, Edward; Harada, Eric T.; Pollard, James; Bhat, Ashwini; Cech, Cynthia; Yang, Alexander; Arnold, Cleoma; Palla, Mirkó; Hovis, Jennifer; Chen, Roger; Morozova, Irina; Kalachikov, Sergey; Russo, James J.; Kasianowicz, John J.; Davis, Randy; Roever, Stefan; Church, George M.; Ju, Jingyue

2016-01-01

DNA sequencing by synthesis (SBS) offers a robust platform to decipher nucleic acid sequences. Recently, we reported a single-molecule nanopore-based SBS strategy that accurately distinguishes four bases by electronically detecting and differentiating four different polymer tags attached to the 5′-phosphate of the nucleotides during their incorporation into a growing DNA strand catalyzed by DNA polymerase. Further developing this approach, we report here the use of nucleotides tagged at the terminal phosphate with oligonucleotide-based polymers to perform nanopore SBS on an α-hemolysin nanopore array platform. We designed and synthesized several polymer-tagged nucleotides using tags that produce different electrical current blockade levels and verified they are active substrates for DNA polymerase. A highly processive DNA polymerase was conjugated to the nanopore, and the conjugates were complexed with primer/template DNA and inserted into lipid bilayers over individually addressable electrodes of the nanopore chip. When an incoming complementary-tagged nucleotide forms a tight ternary complex with the primer/template and polymerase, the tag enters the pore, and the current blockade level is measured. The levels displayed by the four nucleotides tagged with four different polymers captured in the nanopore in such ternary complexes were clearly distinguishable and sequence-specific, enabling continuous sequence determination during the polymerase reaction. Thus, real-time single-molecule electronic DNA sequencing data with single-base resolution were obtained. The use of these polymer-tagged nucleotides, combined with polymerase tethering to nanopores and multiplexed nanopore sensors, should lead to new high-throughput sequencing methods. PMID:27091962

Brittle-to-ductile transition of lithiated silicon electrodes: Crazing to stable nanopore growth.

PubMed

Wang, Haoran; Wang, Xueju; Xia, Shuman; Chew, Huck Beng

2015-09-14

Using first principle calculations, we uncover the underlying mechanisms explaining the brittle-to-ductile transition of LixSi electrodes in lithium ion batteries with increasing Li content. We show that plasticity initiates at x = ∼ 0.5 with the formation of a craze-like network of nanopores separated by Si-Si bonds, while subsequent failure is still brittle-like with the breaking of Si-Si bonds. Transition to ductile behavior occurs at x ⩾ 1 due to the increased density of highly stretchable Li-Li bonds, which delays nanopore formation and stabilizes nanopore growth. Collapse of the nanopores during unloading of the LixSi alloys leads to significant strain recovery.

An overview on the characterization and mechanical behavior of nanoporous Gold

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hodge, A M; Hayes, J R; Caro, J A

2005-09-13

In this paper we present what we believe are the most pressing issues in understanding the mechanical behavior of nanoporous foams. We have postulated that a gold foam presents the best candidate for a systematic study of nanoporous foams since it can be synthesized with a wide range of ligaments sizes and densities. We have also conducted preliminary tests that demonstrate (a) Au foams have a fracture behavior dictated by the ligament size, and (b) nanoporous Au is a high yield strength material. Thus, we have demonstrated the potential in developing nanoporous foams as a new class of high yieldmore » strength/low density materials.« less

Nanopore fabrication and characterization by helium ion microscopy

NASA Astrophysics Data System (ADS)

Emmrich, D.; Beyer, A.; Nadzeyka, A.; Bauerdick, S.; Meyer, J. C.; Kotakoski, J.; Gölzhäuser, A.

2016-04-01

The Helium Ion Microscope (HIM) has the capability to image small features with a resolution down to 0.35 nm due to its highly focused gas field ionization source and its small beam-sample interaction volume. In this work, the focused helium ion beam of a HIM is utilized to create nanopores with diameters down to 1.3 nm. It will be demonstrated that nanopores can be milled into silicon nitride, carbon nanomembranes, and graphene with well-defined aspect ratio. To image and characterize the produced nanopores, helium ion microscopy and high resolution scanning transmission electron microscopy were used. The analysis of the nanopores' growth behavior allows inferring on the profile of the helium ion beam.

Synthesis and applications of nanoporous perovskite metal oxides

PubMed Central

Huang, Xiubing; Zhao, Guixia

2018-01-01

Perovskite-type metal oxides have been widely investigated and applied in various fields in the past several decades due to their extraordinary variability of compositions and structures with targeted physical and chemical properties (e.g., redox behaviour, oxygen mobility, electronic and ionic conductivity). Recently, nanoporous perovskite metal oxides have attracted extensive attention because of their special morphology and properties, as well as superior performance. This minireview aims at summarizing and reviewing the different synthesis methods of nanoporous perovskite metal oxides and their various applications comprehensively. The correlations between the nanoporous structures and the specific performance of perovskite oxides are summarized and highlighted. The future research directions of nanoporous perovskite metal oxides are also prospected. PMID:29862001

Thermal Conductivity in Nanoporous Gold Films during Electron-Phonon Nonequilibrium

DOE PAGES

Hopkins, Patrick E.; Norris, Pamela M.; Phinney, Leslie M.; ...

2008-01-01

The reduction of nanodevices has given recent attention to nanoporous materials due to their structure and geometry. However, the thermophysical properties of these materials are relatively unknown. In this article, an expression for thermal conductivity of nanoporous structures is derived based on the assumption that the finite size of the ligaments leads to electron-ligament wall scattering. This expression is then used to analyze the thermal conductivity of nanoporous structures in the event of electron-phonon nonequilibrium.

Biomimetic Mineralization of Gold Nanoclusters as Multifunctional Thin Films for Glass Nanopore Modification, Characterization, and Sensing.

PubMed

Cao, Sumei; Ding, Shushu; Liu, Yingzi; Zhu, Anwei; Shi, Guoyue

2017-08-01

Hurdles of nanopore modification and characterization restrain the development of glass capillary-based nanopore sensing platforms. In this article, a simple but effective biomimetic mineralization method was developed to decorate glass nanopore with a thin film of bovine serum albumin-protected Au nanocluster (BSA-Au NC). The BSA-Au NC film emitted a strong red fluorescence whereby nondestructive characterization of Au film decorated at the inner surface of glass nanopore can be facilely achieved by a fluorescence microscopy. Besides, the BSA molecules played dual roles in the fabrication of functionalized Au thin film in glass nanopore: they not only directed the synthesis of fluorescent Au thin film but also provided binding sites for recognition, thus achieving synthesis-modification integration. This occurred due to the ionized carboxyl groups (-COO - ) of a BSA coating layer on Au NCs which can interacted with arginine (Arg) via guanidinium groups. The added Arg selectively led to the change in the charge and ionic current of BSA-Au NC film-decorated glass nanopore. Such ionic current responses can be used for quantifying Arg with a detection limit down to 1 fM, which was more sensitive than that of previous sensing systems. Together, the designed method exhibited great promise in providing a facile and controllable solution for glass nanopore modification, characterization, and sensing.

Formation of self-organized nanoporous anodic oxide from metallic gallium.

PubMed

Pandey, Bipin; Thapa, Prem S; Higgins, Daniel A; Ito, Takashi

2012-09-25

This paper reports the formation of self-organized nanoporous gallium oxide by anodization of solid gallium metal. Because of its low melting point (ca. 30 °C), metallic gallium can be shaped into flexible structures, permitting the fabrication of nanoporous anodic oxide monoliths within confined spaces like the inside of a microchannel. Here, solid gallium films prepared on planar substrates were employed to investigate the effects of anodization voltage (1, 5, 10, 15 V) and H(2)SO(4) concentration (1, 2, 4, 6 M) on anodic oxide morphology. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H(2)SO(4) at 10 and 15 V. Nanopore formation could be recognized by an increase in anodic current after a current decrease reflecting barrier oxide formation. The average pore diameter was in the range of 18-40 nm with a narrow diameter distribution (relative standard deviation ca. 10-20%), and was larger at lower H(2)SO(4) concentration and higher applied voltage. The maximum thickness of nanoporous anodic oxide was ca. 2 μm. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis.

Signal and Noise in FET-Nanopore Devices.

PubMed

Parkin, William M; Drndić, Marija

2018-02-23

The combination of a nanopore with a local field-effect transistor (FET-nanopore), like a nanoribbon, nanotube, or nanowire, in order to sense single molecules translocating through the pore is promising for DNA sequencing at megahertz bandwidths. Previously, it was experimentally determined that the detection mechanism was due to local potential fluctuations that arise when an analyte enters a nanopore and constricts ion flow through it, rather than the theoretically proposed mechanism of direct charge coupling between the DNA and nanowire. However, there has been little discussion on the experimentally observed detection mechanism and its relation to the operation of real devices. We model the intrinsic signal and noise in such an FET-nanopore device and compare the results to the ionic current signal. The physical dimensions of DNA molecules limit the change in gate voltage on the FET to below 40 mV. We discuss the low-frequency flicker noise (<10 kHz), medium-frequency thermal noise (<100 kHz), and high-frequency capacitive noise (>100 kHz) in FET-nanopore devices. At bandwidths dominated by thermal noise, the signal-to-noise ratio in FET-nanopore devices is lower than in the ionic current signal. At high frequencies, where noise due to parasitic capacitances in the amplifier and chip is the dominant source of noise in ionic current measurements, high-transconductance FET-nanopore devices can outperform ionic current measurements.

Nanopatterned polystyrene-b-poly(acrylic acid) surfaces to modulate cell-material interaction.

PubMed

Lizundia, Erlantz; Sáenz-Pérez, Míriam; Patrocinio, David; Aurrekoetxea, Iskander; dM Vivanco, Maria; Vilas, José Luis

2017-06-01

In this work we explore the effect of surface nanoarchitecture of polystyrene (PS) and polystyrene-b-poly(acrylic acid) (PS-b-PAA) diblock copolymer films on cell viability. PS and PS-b-PAA have been nanopatterned at temperatures of 110, 120 and 140°C using nanoporous aluminium oxide membranes (AAO) as a template. Surface architecture strongly depends on the infiltration temperature and the nature of the infiltrated polymer. High patterning temperatures yield hollow fibre shape architecture at the nanoscale level, which substantially modifies the surface hydrophobicity of the resulting materials. Up to date very scarce reports could be found in the literature dealing with the interaction of microstructured/nanostructured polymeric surfaces with cancer cells. Therefore, MCF-7 breast cancer cells have been selected as a model to conduct cell viability assays. The findings reveal that the fine-tuning of the surface nanoarchitecture contributes to the modification of its biocompatibility. Overall, this study highlights the potential of AAO membranes to obtain well-defined tailored morphologies at nanoscale level and its importance to develop novel soft functional surfaces to be used in the biomedical field. Copyright © 2017 Elsevier B.V. All rights reserved.

Integration of solid-state nanopores in a 0.5 μm CMOS foundry process.

PubMed

Uddin, A; Yemenicioglu, S; Chen, C-H; Corigliano, E; Milaninia, K; Theogarajan, L

2013-04-19

High-bandwidth and low-noise nanopore sensor and detection electronics are crucial in achieving single-DNA-base resolution. A potential way to accomplish this goal is to integrate solid-state nanopores within a CMOS platform, in close proximity to the biasing electrodes and custom-designed amplifier electronics. Here we report the integration of solid-state nanopore devices in a commercial complementary metal-oxide-semiconductor (CMOS) potentiostat chip implemented in On-Semiconductor's 0.5 μm technology. Nanopore membranes incorporating electrodes are fabricated by post-CMOS micromachining utilizing the n+ polysilicon/SiO2/n+ polysilicon capacitor structure available in the aforementioned process. Nanopores are created in the CMOS process by drilling in a transmission electron microscope and shrinking by atomic layer deposition. We also describe a batch fabrication method to process a large of number of electrode-embedded nanopores with sub-10 nm diameter across CMOS-compatible wafers by electron beam lithography and atomic layer deposition. The CMOS-compatibility of our fabrication process is verified by testing the electrical functionality of on-chip circuitry. We observe high current leakage with the CMOS nanopore devices due to the ionic diffusion through the SiO2 membrane. To prevent this leakage, we coat the membrane with Al2O3, which acts as an efficient diffusion barrier against alkali ions. The resulting nanopore devices also exhibit higher robustness and lower 1/f noise as compared to SiO2 and SiNx. Furthermore, we propose a theoretical model for our low-capacitance CMOS nanopore devices, showing good agreement with the experimental value. In addition, experiments and theoretical models of translocation studies are presented using 48.5 kbp λ-DNA in order to prove the functionality of on-chip pores coated with Al2O3.

Streaming current magnetic fields in a charged nanopore.

PubMed

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W

2016-11-11

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques.

Simultaneous Ionic Current and Potential Detection of Nanoparticles by a Multifunctional Nanopipette.

PubMed

Panday, Namuna; Qian, Gongming; Wang, Xuewen; Chang, Shuai; Pandey, Popular; He, Jin

2016-12-27

Nanopore sensing-based technologies have made significant progress for single molecule and single nanoparticle detection and analysis. In recent years, multimode sensing by multifunctional nanopores shows the potential to greatly improve the sensitivity and selectivity of traditional resistive-pulse sensing methods. In this paper, we showed that two label-free electric sensing modes could work cooperatively to detect the motion of 40 nm diameter spherical gold nanoparticles (GNPs) in solution by a multifunctional nanopipette. The multifunctional nanopipettes containing both nanopore and nanoelectrode (pyrolytic carbon) at the tip were fabricated quickly and cheaply. We demonstrated that the ionic current and local electrical potential changes could be detected simultaneously during the translocation of individual GNPs. We also showed that the nanopore/CNE tip geometry enabled the CNE not only to detect the translocation of single GNP but also to collectively detect several GNPs outside the nanopore entrance. The dynamic accumulation of GNPs near the nanopore entrance resulted in no detectable current changes, but was detected by the potential changes at the CNE. We revealed the motions of GNPs both outside and inside the nanopore, individually and collectively, with the combination of ionic current and potential measurements.

Detecting the Length of Double-stranded DNA with Solid State Nanopores

NASA Astrophysics Data System (ADS)

Li, Jiali; Gershow, Marc; Stein, Derek; Qun, Cai; Brandin, Eric; Wang, Hui; Huang, Albert; Branton, Dan; Golovchenko, Jene

2003-03-01

We report on the use of nanometer scale diameter, solid-state nanopores as single molecule detectors of double stranded DNA molecules. These solid-state nanopores are fabricated in thin membranes of silicon nitride, by ion beam sculpting 1. They produce discrete electronic signals: current blockages, when an electrically biased nanopore is exposed to DNA molecules in aqueous salt solutions. We demonstrate examples of such electronic signals for 3k base pairs (bp) and 10k bp double stranded DNA molecules, which suggest that these molecules are individually translocating through the nanopore during the detection process. The translocating time for the 10k bp double stranded DNA is about 3 times longer than the 3k bp, demonstrating that a solid-state nanopore device can be used to detect the lengths of double stranded DNA molecules. Similarities and differences with signals obtained from single stranded DNA in a biological nanopores are discussed 2. 1. Li, J., Stein, D., McMullan, C., Branton, D. Aziz, M. J. and Golovchenko, J. Ion Beam Sculpting at nanometer length scales. Nature 412, 166-169 (2001). 2. Meller, A., L. Nivon, E. Brandin, Golovchenko, J. & Branton, D. Proc. Natl. Acad. Sci. USA 97, 1079-1084 (2000).

Theory for polymer analysis using nanopore-based single-molecule mass spectrometry

PubMed Central

Reiner, Joseph E.; Kasianowicz, John J.; Nablo, Brian J.; Robertson, Joseph W. F.

2010-01-01

Nanometer-scale pores have demonstrated potential for the electrical detection, quantification, and characterization of molecules for biomedical applications and the chemical analysis of polymers. Despite extensive research in the nanopore sensing field, there is a paucity of theoretical models that incorporate the interactions between chemicals (i.e., solute, solvent, analyte, and nanopore). Here, we develop a model that simultaneously describes both the current blockade depth and residence times caused by individual poly(ethylene glycol) (PEG) molecules in a single α-hemolysin ion channel. Modeling polymer-cation binding leads to a description of two significant effects: a reduction in the mobile cation concentration inside the pore and an increase in the affinity between the polymer and the pore. The model was used to estimate the free energy of formation for K+-PEG inside the nanopore (≈-49.7 meV) and the free energy of PEG partitioning into the nanopore (≈0.76 meV per ethylene glycol monomer). The results suggest that rational, physical models for the analysis of analyte-nanopore interactions will develop the full potential of nanopore-based sensing for chemical and biological applications. PMID:20566890

Streaming current magnetic fields in a charged nanopore

NASA Astrophysics Data System (ADS)

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W.

2016-11-01

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques.

Nanopore arrays in a silicon membrane for parallel single-molecule detection: DNA translocation

NASA Astrophysics Data System (ADS)

Zhang, Miao; Schmidt, Torsten; Jemt, Anders; Sahlén, Pelin; Sychugov, Ilya; Lundeberg, Joakim; Linnros, Jan

2015-08-01

Optical nanopore sensing offers great potential in single-molecule detection, genotyping, or DNA sequencing for high-throughput applications. However, one of the bottle-necks for fluorophore-based biomolecule sensing is the lack of an optically optimized membrane with a large array of nanopores, which has large pore-to-pore distance, small variation in pore size and low background photoluminescence (PL). Here, we demonstrate parallel detection of single-fluorophore-labeled DNA strands (450 bps) translocating through an array of silicon nanopores that fulfills the above-mentioned requirements for optical sensing. The nanopore array was fabricated using electron beam lithography and anisotropic etching followed by electrochemical etching resulting in pore diameters down to ∼7 nm. The DNA translocation measurements were performed in a conventional wide-field microscope tailored for effective background PL control. The individual nanopore diameter was found to have a substantial effect on the translocation velocity, where smaller openings slow the translocation enough for the event to be clearly detectable in the fluorescence. Our results demonstrate that a uniform silicon nanopore array combined with wide-field optical detection is a promising alternative with which to realize massively-parallel single-molecule detection.

Nanoporous polymer electrolyte

DOEpatents

Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

2012-04-24

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

Computational modeling and analysis of thermoelectric properties of nanoporous silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, H.; Yu, Y.; Li, G., E-mail: gli@clemson.edu

2014-03-28

In this paper, thermoelectric properties of nanoporous silicon are modeled and studied by using a computational approach. The computational approach combines a quantum non-equilibrium Green's function (NEGF) coupled with the Poisson equation for electrical transport analysis, a phonon Boltzmann transport equation (BTE) for phonon thermal transport analysis and the Wiedemann-Franz law for calculating the electronic thermal conductivity. By solving the NEGF/Poisson equations self-consistently using a finite difference method, the electrical conductivity σ and Seebeck coefficient S of the material are numerically computed. The BTE is solved by using a finite volume method to obtain the phonon thermal conductivity k{sub p}more » and the Wiedemann-Franz law is used to obtain the electronic thermal conductivity k{sub e}. The figure of merit of nanoporous silicon is calculated by ZT=S{sup 2}σT/(k{sub p}+k{sub e}). The effects of doping density, porosity, temperature, and nanopore size on thermoelectric properties of nanoporous silicon are investigated. It is confirmed that nanoporous silicon has significantly higher thermoelectric energy conversion efficiency than its nonporous counterpart. Specifically, this study shows that, with a n-type doping density of 10{sup 20} cm{sup –3}, a porosity of 36% and nanopore size of 3 nm × 3 nm, the figure of merit ZT can reach 0.32 at 600 K. The results also show that the degradation of electrical conductivity of nanoporous Si due to the inclusion of nanopores is compensated by the large reduction in the phonon thermal conductivity and increase of absolute value of the Seebeck coefficient, resulting in a significantly improved ZT.« less

Electrochemical Generation of a Hydrogen Bubble at a Recessed Platinum Nanopore Electrode.

PubMed

Chen, Qianjin; Luo, Long; White, Henry S

2015-04-21

We report the electrochemical generation of a single hydrogen bubble within the cavity of a recessed Pt nanopore electrode. The recessed Pt electrode is a conical pore in glass that contains a micrometer-scale Pt disk (1-10 μm radius) at the nanopore base and a nanometer-scale orifice (10-100 nm radius) that restricts diffusion of electroactive molecules and dissolved gas between the nanopore cavity and bulk solution. The formation of a H2 bubble at the Pt disk electrode in voltammetric experiments results from the reduction of H(+) in a 0.25 M H2SO4 solution; the liquid-to-gas phase transformation is indicated in the voltammetric response by a precipitous decrease in the cathodic current due to rapid bubble nucleation and growth within the nanopore cavity. Finite element simulations of the concentration distribution of dissolved H2 within the nanopore cavity, as a function of the H(+) reduction current, indicate that H2 bubble nucleation at the recessed Pt electrode surface occurs at a critical supersaturation concentration of ∼0.22 M, in agreement with the value previously obtained at (nonrecessed) Pt disk electrodes (∼0.25 M). Because the nanopore orifice limits the diffusion of H2 out of the nanopore cavity, an anodic peak corresponding to the oxidation of gaseous and dissolved H2 trapped in the recessed cavity is readily observed on the reverse voltammetric scan. Integration of the charge associated with the H2 oxidation peak is found to approach that of the H(+) reduction peak at high scan rates, confirming the assignment of the anodic peak to H2 oxidation. Preliminary results for the electrochemical generation of O2 bubbles from water oxidation at a recessed nanopore electrode are consistent with the electrogeneration of H2 bubbles.

Nanopore-based fourth-generation DNA sequencing technology.

PubMed

Feng, Yanxiao; Zhang, Yuechuan; Ying, Cuifeng; Wang, Deqiang; Du, Chunlei

2015-02-01

Nanopore-based sequencers, as the fourth-generation DNA sequencing technology, have the potential to quickly and reliably sequence the entire human genome for less than $1000, and possibly for even less than $100. The single-molecule techniques used by this technology allow us to further study the interaction between DNA and protein, as well as between protein and protein. Nanopore analysis opens a new door to molecular biology investigation at the single-molecule scale. In this article, we have reviewed academic achievements in nanopore technology from the past as well as the latest advances, including both biological and solid-state nanopores, and discussed their recent and potential applications. Copyright © 2015 The Authors. Production and hosting by Elsevier Ltd.. All rights reserved.

Coordinative nanoporous polymers synthesized with hydrogen-bonded columnar liquid crystals.

PubMed

Ishihara, Shinsuke; Furuki, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Takeoka, Shinji

2012-10-01

In this paper, we report the development of nanoporous polymer which demonstrates the coordination property toward zinc porphyrin. A hydrogen-bonded columnar liquid crystalline precursor composed of a triphenylene template and three equivalent of the surrounding dendric amphiphile bearing a pyridyl head group and a polymerizable aliphatic chain, was covalently fixed by photopolymerization, and then the subsequent selective removal of the template successively resulted in a nanoporous polymer in which the pore wall is modified with pyridyl groups. The nanoporous polymer reflected the conformation of template, and displayed considerable coordination ability of the pyridyl groups towards zinc porphyrin. The coordinative nanoporous polymer is promising as a nano-scaled scaffold for the organization of dyes into functional supramolecular architectures.

Aptamer-Encoded Nanopore for Ultrasensitive Detection of Bioterrorist Agent Ricin at Single-Molecule Resolution

PubMed Central

Gu, Li-Qun; Ding, Shu; Gao, Changlu

2011-01-01

The molecular-scale pore structure, called nanopore, can be formed from protein ion channels by genetic engineering or fabricated on solid substrates using fashion nanotechnology. Target molecules in interaction with the functionalized lumen of nanopore, can produce characteristic changes in the pore conductance, which act as fingerprints, allowing us to identify single molecules and simultaneously quantify each target species in the mixture. Nanopore sensors have been created for tremendous biomedical detections, with targets ranging from metal ions, drug compounds and cellular second messengers, to proteins and DNAs. Here we will review our recent discoveries with a lab-in-hand glass nanopore: single-molecule discrimination of chiral enantiomers with a trapped cyclodextrin, and sensing of bioterrorist agent ricin. PMID:19964179

Method to fabricate functionalized conical nanopores

DOEpatents

Small, Leo J.; Spoerke, Erik David; Wheeler, David R.

2016-07-12

A pressure-based chemical etch method is used to shape polymer nanopores into cones. By varying the pressure, the pore tip diameter can be controlled, while the pore base diameter is largely unaffected. The method provides an easy, low-cost approach for conically etching high density nanopores.

Fabrication and characterization of a solid state nanopore with self-aligned carbon nanoelectrodes for molecular detection

NASA Astrophysics Data System (ADS)

Spinney, Patrick; Collins, Scott D.; Howitt, David G.; Smith, Rosemary L.

2012-06-01

Rapid and cost-effective DNA sequencing is a pivotal prerequisite for the genomics era. Many of the recent advances in forensics, medicine, agriculture, taxonomy, and drug discovery have paralleled critical advances in DNA sequencing technology. Nanopore modalities for DNA sequencing have recently surfaced including the electrical interrogation of protein ion channels and/or solid-state nanopores during translocation of DNA. However to date, most of this work has met with mixed success. In this work, we present a unique nanofabrication strategy that realizes an artificial nanopore articulated with carbon electrodes to sense the current modulations during the transport of DNA through the nanopore. This embodiment overcomes most of the technical difficulties inherent in other artificial nanopore embodiments and present a versatile platform for the testing of DNA single nucleotide detection. Characterization of the device using gold nanoparticles, silica nanoparticles, lambda dsDNA and 16-mer ssDNA are presented. Although single molecule DNA sequencing is still not demonstrated, the device shows a path towards this goal.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

PubMed

Jung, Hun Bok; Boyanov, Maxim I; Konishi, Hiromi; Sun, Yubing; Mishra, Bhoopesh; Kemner, Kenneth M; Roden, Eric E; Xu, Huifang

2012-07-03

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Non-sticky translocation of bio-molecules through Tween 20-coated solid-state nanopores in a wide pH range

NASA Astrophysics Data System (ADS)

Li, Xiaoqing; Hu, Rui; Li, Ji; Tong, Xin; Diao, J. J.; Yu, Dapeng; Zhao, Qing

2016-10-01

Nanopore-based sensing technology is considered high-throughput and low-cost for single molecule detection, but solid-state nanopores have suffered from pore clogging issues. A simple Tween 20 coating method is applied to ensure long-term (several hours) non-sticky translocation of various types of bio-molecules through SiN nanopores in a wide pH range (4.0-13.0). We also emphasize the importance of choosing appropriate concentration of Tween 20 coating buffer for desired effect. By coating nanopores with a Tween 20 layer, we are able to differentiate between single-stranded DNA and double-stranded DNA, to identify drift-dominated domain for single-stranded DNA, to estimate BSA volume and to observe the shape of individual nucleosome translocation event without non-specific adsorption. The wide pH endurance from 4.0 to 13.0 and the broad types of detection analytes including nucleic acids, proteins, and biological complexes highlight the great application potential of Tween 20-coated solid-state nanopores.

Single molecule transistor based nanopore for the detection of nicotine

NASA Astrophysics Data System (ADS)

Ray, S. J.

2014-12-01

A nanopore based detection methodology was proposed and investigated for the detection of Nicotine. This technique uses a Single Molecular Transistor working as a nanopore operational in the Coulomb Blockade regime. When the Nicotine molecule is pulled through the nanopore area surrounded by the Source(S), Drain (D), and Gate electrodes, the charge stability diagram can detect the presence of the molecule and is unique for a specific molecular structure. Due to the weak coupling between the different electrodes which is set by the nanopore size, the molecular energy states stay almost unaffected by the electrostatic environment that can be realised from the charge stability diagram. Identification of different orientation and position of the Nicotine molecule within the nanopore area can be made from specific regions of overlap between different charge states on the stability diagram that could be used as an electronic fingerprint for detection. This method could be advantageous and useful to detect the presence of Nicotine in smoke which is usually performed using chemical chromatography techniques.

Integrated nanopore sensing platform with sub-microsecond temporal resolution

PubMed Central

Rosenstein, Jacob K; Wanunu, Meni; Merchant, Christopher A; Drndic, Marija; Shepard, Kenneth L

2012-01-01

Nanopore sensors have attracted considerable interest for high-throughput sensing of individual nucleic acids and proteins without the need for chemical labels or complex optics. A prevailing problem in nanopore applications is that the transport kinetics of single biomolecules are often faster than the measurement time resolution. Methods to slow down biomolecular transport can be troublesome and are at odds with the natural goal of high-throughput sensing. Here we introduce a low-noise measurement platform that integrates a complementary metal-oxide semiconductor (CMOS) preamplifier with solid-state nanopores in thin silicon nitride membranes. With this platform we achieved a signal-to-noise ratio exceeding five at a bandwidth of 1 MHz, which to our knowledge is the highest bandwidth nanopore recording to date. We demonstrate transient signals as brief as 1 μs from short DNA molecules as well as current signatures during molecular passage events that shed light on submolecular DNA configurations in small nanopores. PMID:22426489

Mean force potential of interaction between Na+ and Cl- ions in planar nanopores in contact with water under pressure

NASA Astrophysics Data System (ADS)

Shevkunov, S. V.

2017-11-01

The mean force potential (MFP) of interaction between counterions Na+ and Cl- in a planar nanopore with structureless hydrophobic walls is calculated via computer simulation under the condition that the nanopore is in contact with water at an external pressure that exceeds the saturation pressure but remains insufficient to fill the nanopore with water. For a nanopore with a liquid phase, the MFP dependence on the interionic distance indicates the dissociation of an ion pair into two hydrated ions in a nanopore that is not completely filled with water. Fluctuations in the number of water molecules drawn into the interionic space decisively influence the dissociation. The attraction between counterions, averaged over thermal fluctuations, depends largely on the pore width and grows as the shielding of the ions' electric field by water molecules in a narrow pore diminishes. The contributions from energy and entropy to the free energy of hydration are analyzed.

Fabrication of high reflectivity nanoporous distributed Bragg reflectors by controlled electrochemical etching of GaN

NASA Astrophysics Data System (ADS)

Lee, Seung-Min; Kang, Jin-Ho; Lee, June Key; Ryu, Sang-Wan

2016-09-01

The nanoporous medium is a valuable feature of optical devices because of its variable optical refractive index with porosity. One important application is in a GaN-based vertical cavity surface emitting laser having a distributed Bragg reflector (DBR) composed of alternating nanoporous and bulk GaNs. However, optimization of the fabrication process for high reflectivity DBRs having wellcontrolled high reflection bands has not been studied yet. We used electrochemical etching to study the fabrication process of a nanoporous GaN DBR and analyzed the relationship between the morphology and optical reflectivity. Several electrolytes were examined for the formation of the optimized nanoporous structure. A highly reflective DBRs having reflectivity of ~100% were obtained over a wide wavelength range of 450-750 nm. Porosification of semiconductors into nanoporous layers could provide a high reflectivity DBR due to controlled index-contrast, which would be advantages for the construction of a high-Q optical cavity.

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors.

PubMed

Prasad, Kumaresa P S; Dhawale, Dattatray S; Sivakumar, Thiripuranthagan; Aldeyab, Salem S; Zaidi, Javaid S M; Ariga, Katsuhiko; Vinu, Ajayan

2011-08-01

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g -1 at a 20 mV s -1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

NASA Astrophysics Data System (ADS)

Prasad, Kumaresa P. S.; Dhawale, Dattatray S.; Sivakumar, Thiripuranthagan; Aldeyab, Salem S.; Zaidi, Javaid S. M.; Ariga, Katsuhiko; Vinu, Ajayan

2011-08-01

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g-1 at a 20 mV s-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.

Modulation of Molecular Flux Using a Graphene Nanopore Capacitor.

PubMed

Shankla, Manish; Aksimentiev, Aleksei

2017-04-20

Modulation of ionic current flowing through nanoscale pores is one of the fundamental biological processes. Inspired by nature, nanopores in synthetic solid-state membranes are being developed to enable rapid analysis of biological macromolecules and to serve as elements of nanofludic circuits. Here, we theoretically investigate ion and water transport through a graphene-insulator-graphene membrane containing a single, electrolyte-filled nanopore. By means of all-atom molecular dynamics simulations, we show that the charge state of such a graphene nanopore capacitor can regulate both the selectivity and the magnitude of the nanopore ionic current. At a fixed transmembrane bias, the ionic current can be switched from being carried by an equal mixture of cations and anions to being carried almost exclusively by either cationic or anionic species, depending on the sign of the charge assigned to both plates of the capacitor. Assigning the plates of the capacitor opposite sign charges can either increase the nanopore current or reduce it substantially, depending on the polarity of the bias driving the transmembrane current. Facilitated by the changes of the nanopore surface charge, such ionic current modulations are found to occur despite the physical dimensions of the nanopore being an order of magnitude larger than the screening length of the electrolyte. The ionic current rectification is accompanied by a pronounced electro-osmotic effect that can transport neutral molecules such as proteins and drugs across the solid-state membrane and thereby serve as an interface between electronic and chemical signals.

Identification of Essential Sensitive Regions of the Aerolysin Nanopore for Single Oligonucleotide Analysis.

PubMed

Wang, Ya-Qian; Li, Meng-Yin; Qiu, Hu; Cao, Chan; Wang, Ming-Bo; Wu, Xue-Yuan; Huang, Jin; Ying, Yi-Lun; Long, Yi-Tao

2018-06-11

The aerolysin nanopore channel is one of the confined spaces for single molecule analysis which displays high spatial and temporal resolution for the discrimination of single nucleotides, identification of DNA base modification, and analyzing the structural transition of DNAs. However, to overcome the challenge of achieving the ultimate goal of the widespread real analytical application, it is urgent to probe the sensing regions of the aerolysin to further improve the sensitivity. In this paper, we explore the sensing regions of the aerolysin nanopore by a series of well-designed mutant nanopore experiments combined with molecular dynamics simulations-based electrostatic analysis. The positively charged lumen-exposed Lys-238, identified as one of the key sensing sites due to the presence of a deep valley in the electrostatic potentials, was replaced by different charged and sized amino acids. The results show that the translocation time of oligonucleotides through the nanopore can be readily modulated by the choice of the target amino acid at the 238 site. In particular, a 7-fold slower translocation at a voltage bias of +120 mV is observed with respect to the wild-type aerolysin, which provides a high resolution for methylated cytosine discrimination. We further determine that both the electrostatic properties and geometrical structure of the aerolysin nanopore are crucial to its sensing ability. These insights open ways for rationally designing the sensing mechanism of the aerolysin nanopore, thus providing a novel paradigm for nanopore sensing.

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

PubMed Central

Prasad, Kumaresa P S; Dhawale, Dattatray S; Sivakumar, Thiripuranthagan; Aldeyab, Salem S; Zaidi, Javaid S M; Ariga, Katsuhiko; Vinu, Ajayan

2011-01-01

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g-1 at a 20 mV s-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles. PMID:27877410

Method of making nanostructured glass-ceramic waste forms

DOEpatents

Gao, Huizhen; Wang, Yifeng; Rodriguez, Mark A.; Bencoe, Denise N.

2012-12-18

A method of rendering hazardous materials less dangerous comprising trapping the hazardous material in nanopores of a nanoporous composite material, reacting the trapped hazardous material to render it less volatile/soluble, sealing the trapped hazardous material, and vitrifying the nanoporous material containing the less volatile/soluble hazardous material.

DNA translocation measurements in solid-state nanopores fabricated using helium-ion microscope

NASA Astrophysics Data System (ADS)

Liu, Liping; Miao, Wang; Huynh, Chuong; Liu, Quanjun; Ling, Xinsheng

2012-02-01

We report high-quality DNA translocation measurements in solid-state nanopores drilled in free-standing SiN membranes by using a helium-ion beam in a Zeiss helium-ion microscope (HIM). We show that the HIM nanopores have similar performance as the TEM-drilled pores.

Method of making nanostructured glass-ceramic waste forms

DOEpatents

Gao, Huizhen; Wang, Yifeng; Rodriguez, Mark A.; Bencoe, Denise N.

2014-07-08

A waste form for and a method of rendering hazardous materials less dangerous is disclosed that includes fixing the hazardous material in nanopores of a nanoporous material, reacting the trapped hazardous material to render it less volatile/soluble, and vitrifying the nanoporous material containing the less volatile/soluble hazardous material.

Rapid and precise scanning helium ion microscope milling of solid-state nanopores for biomolecule detection.

PubMed

Yang, Jijin; Ferranti, David C; Stern, Lewis A; Sanford, Colin A; Huang, Jason; Ren, Zheng; Qin, Lu-Chang; Hall, Adam R

2011-07-15

We report the formation of solid-state nanopores using a scanning helium ion microscope. The fabrication process offers the advantage of high sample throughput along with fine control over nanopore dimensions, producing single pores with diameters below 4 nm. Electronic noise associated with ion transport through the resultant pores is found to be comparable with levels measured on devices made with the established technique of transmission electron microscope milling. We demonstrate the utility of our nanopores for biomolecular analysis by measuring the passage of double-strand DNA.

Nanopores and nucleic acids: prospects for ultrarapid sequencing

NASA Technical Reports Server (NTRS)

Deamer, D. W.; Akeson, M.

2000-01-01

DNA and RNA molecules can be detected as they are driven through a nanopore by an applied electric field at rates ranging from several hundred microseconds to a few milliseconds per molecule. The nanopore can rapidly discriminate between pyrimidine and purine segments along a single-stranded nucleic acid molecule. Nanopore detection and characterization of single molecules represents a new method for directly reading information encoded in linear polymers. If single-nucleotide resolution can be achieved, it is possible that nucleic acid sequences can be determined at rates exceeding a thousand bases per second.

Tunable graphene quantum point contact transistor for DNA detection and characterization

PubMed Central

Girdhar, Anuj; Sathe, Chaitanya; Schulten, Klaus; Leburton, Jean-Pierre

2015-01-01

A graphene membrane conductor containing a nanopore in a quantum point contact (QPC) geometry is a promising candidate to sense, and potentially sequence, DNA molecules translocating through the nanopore. Within this geometry, the shape, size, and position of the nanopore as well as the edge configuration influences the membrane conductance caused by the electrostatic interaction between the DNA nucleotides and the nanopore edge. It is shown that the graphene conductance variations resulting from DNA translocation can be enhanced by choosing a particular geometry as well as by modulating the graphene Fermi energy, which demonstrates the ability to detect conformational transformations of a double-stranded DNA, as well as the passage of individual base pairs of a single-stranded DNA molecule through the nanopore. PMID:25765702

Characterization of Noble Gas Ion Beam Fabricated Single Molecule Nanopore Detectors

NASA Astrophysics Data System (ADS)

Rollings, Ryan; Ledden, Bradley; Shultz, John; Fologea, Daniel; Li, Jiali; Chervinsky, John; Golovchenko, Jene

2006-03-01

Nanopores fabricated with low energy noble gas ion beams in a silicon nitride membrane can be employed as the fundamental element of single biomolecule detection and characterization devices [1,2]. With the help of X-ray Photoelectron Spectroscopy (XPS) and Rutherford Backscattering (RBS), we demonstrate that the electrical noise properties, and hence ultimate sensitivity of nanopore single molecule detectors depends on ion beam species and nanopore annealing conditions. .1. Li, J., D. Stein, C. McMullan, D. Branton, M.J. Aziz, and J.A. Golovchenko, Ion-beam sculpting at nanometre length scales. Nature, 2001. 412(12 July): p. 166-169. 2. Li, J., M. Gershow, D. Stein, E. Brandin, and J.A. Golovchenko, DNA Molecules and Configurations in a Solid-state Nanopore Microscope. Nature Materials, 2003. 2: p. 611-615.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jin; Fan, Cuncai; Ding, Jie

High energy particle radiations induce severe microstructural damage in metallic materials. Nanoporous materials with a giant surface-to-volume ratio may alleviate radiation damage in irradiated metallic materials as free surface are defect sinks. We show, by using in situ Kr ion irradiation in a transmission electron microscope at room temperature, that nanoporous Au indeed has significantly improved radiation tolerance comparing with coarse-grained, fully dense Au. In situ studies show that nanopores can absorb and eliminate a large number of radiation-induced defect clusters. Meanwhile, nanopores shrink (self-heal) during radiation, and their shrinkage rate is pore size dependent. Furthermore, the in situ studiesmore » show dose-rate-dependent diffusivity of defect clusters. Our study sheds light on the design of radiation-tolerant nanoporous metallic materials for advanced nuclear reactor applications.« less

Fabrication of highly oriented nanoporous fibers via airflow bubble-spinning

NASA Astrophysics Data System (ADS)

Liu, Fujuan; Li, Shaokai; Fang, Yue; Zheng, Fangfang; Li, Junhua; He, Jihuan

2017-11-01

Highly oriented Poly(lactic acid) (PLA) nanofibers with nanoporous structures has been successfully fabricated via airflow bubble-spinning without electrostatic hazard. In this work, the volatile solvent was necessary for preparing the nanoporous fiber, which was attributed to the competition between phase separation and solvent evaporation. The interconnected porous structures were affected by the processing variables of solution concentration, airflow temperature, collecting distance and relative humidity (RH). Besides, the rheological properties of solutions were studied and the highly oriented PLA nanofibers with nanoporous structure were also completely characterized using scanning electron microscope (SEM). This study provided a novel technique that successfully gets rid of the potential safety hazards caused by unexpected static to prepare highly oriented nanoporous fibers, which would demonstrate an impressive prospect for the fields of adsorption and filtration.

Design and characterization of a nanopore-coupled polymerase for single-molecule DNA sequencing by synthesis on an electrode array

PubMed Central

Stranges, P. Benjamin; Palla, Mirkó; Kalachikov, Sergey; Nivala, Jeff; Dorwart, Michael; Trans, Andrew; Kumar, Shiv; Porel, Mintu; Chien, Minchen; Tao, Chuanjuan; Morozova, Irina; Li, Zengmin; Shi, Shundi; Aberra, Aman; Arnold, Cleoma; Yang, Alexander; Aguirre, Anne; Harada, Eric T.; Korenblum, Daniel; Pollard, James; Bhat, Ashwini; Gremyachinskiy, Dmitriy; Bibillo, Arek; Chen, Roger; Davis, Randy; Russo, James J.; Fuller, Carl W.; Roever, Stefan; Ju, Jingyue; Church, George M.

2016-01-01

Scalable, high-throughput DNA sequencing is a prerequisite for precision medicine and biomedical research. Recently, we presented a nanopore-based sequencing-by-synthesis (Nanopore-SBS) approach, which used a set of nucleotides with polymer tags that allow discrimination of the nucleotides in a biological nanopore. Here, we designed and covalently coupled a DNA polymerase to an α-hemolysin (αHL) heptamer using the SpyCatcher/SpyTag conjugation approach. These porin–polymerase conjugates were inserted into lipid bilayers on a complementary metal oxide semiconductor (CMOS)-based electrode array for high-throughput electrical recording of DNA synthesis. The designed nanopore construct successfully detected the capture of tagged nucleotides complementary to a DNA base on a provided template. We measured over 200 tagged-nucleotide signals for each of the four bases and developed a classification method to uniquely distinguish them from each other and background signals. The probability of falsely identifying a background event as a true capture event was less than 1.2%. In the presence of all four tagged nucleotides, we observed sequential additions in real time during polymerase-catalyzed DNA synthesis. Single-polymerase coupling to a nanopore, in combination with the Nanopore-SBS approach, can provide the foundation for a low-cost, single-molecule, electronic DNA-sequencing platform. PMID:27729524

Nanoporous biomaterials for uremic toxin adsorption in artificial kidney systems: A review.

PubMed

Cheah, Wee-Keat; Ishikawa, Kunio; Othman, Radzali; Yeoh, Fei-Yee

2017-07-01

Hemodialysis, one of the earliest artificial kidney systems, removes uremic toxins via diffusion through a semipermeable porous membrane into the dialysate fluid. Miniaturization of the present hemodialysis system into a portable and wearable device to maintain continuous removal of uremic toxins would require that the amount of dialysate used within a closed-system is greatly reduced. Diffused uremic toxins within a closed-system dialysate need to be removed to maintain the optimum concentration gradient for continuous uremic toxin removal by the dialyzer. In this dialysate regenerative system, adsorption of uremic toxins by nanoporous biomaterials is essential. Throughout the years of artificial kidney development, activated carbon has been identified as a potential adsorbent for uremic toxins. Adsorption of uremic toxins necessitates nanoporous biomaterials, especially activated carbon. Nanoporous biomaterials are also utilized in hemoperfusion for uremic toxin removal. Further miniaturization of artificial kidney system and improvements on uremic toxin adsorption capacity would require high performance nanoporous biomaterials which possess not only higher surface area, controlled pore size, but also designed architecture or structure and surface functional groups. This article reviews on various nanoporous biomaterials used in current artificial kidney systems and several emerging nanoporous biomaterials. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1232-1240, 2017. © 2016 Wiley Periodicals, Inc.

Boron Nitride Nanoporous Membranes with High Surface Charge by Atomic Layer Deposition.

PubMed

Weber, Matthieu; Koonkaew, Boonprakrong; Balme, Sebastien; Utke, Ivo; Picaud, Fabien; Iatsunskyi, Igor; Coy, Emerson; Miele, Philippe; Bechelany, Mikhael

2017-05-17

In this work, we report the design and the fine-tuning of boron nitride single nanopore and nanoporous membranes by atomic layer deposition (ALD). First, we developed an ALD process based on the use of BBr 3 and NH 3 as precursors in order to synthesize BN thin films. The deposited films were characterized in terms of thickness, composition, and microstructure. Next, we used the newly developed process to grow BN films on anodic aluminum oxide nanoporous templates, demonstrating the conformality benefit of BN prepared by ALD, and its scalability for the manufacturing of membranes. For the first time, the ALD process was then used to tune the diameter of fabricated single transmembrane nanopores by adjusting the BN thickness and to enable studies of the fundamental aspects of ionic transport on a single nanopore. At pH = 7, we estimated a surface charge density of 0.16 C·m -2 without slip and 0.07 C·m -2 considering a reasonable slip length of 3 nm. Molecular dynamics simulations performed with experimental conditions confirmed the conductivities and the sign of surface charges measured. The high ion transport results obtained and the ability to fine-tune nanoporous membranes by such a scalable method pave the way toward applications such as ionic separation, energy harvesting, and ultrafiltration devices.

Nanoporous thermosetting polymers.

PubMed

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

Streaming current magnetic fields in a charged nanopore

PubMed Central

Mansouri, Abraham; Taheri, Peyman; Kostiuk, Larry W.

2016-01-01

Magnetic fields induced by currents created in pressure driven flows inside a solid-state charged nanopore were modeled by numerically solving a system of steady state continuum partial differential equations, i.e., Poisson, Nernst-Planck, Ampere and Navier-Stokes equations (PNPANS). This analysis was based on non-dimensional transport governing equations that were scaled using Debye length as the characteristic length scale, and applied to a finite length cylindrical nano-channel. The comparison of numerical and analytical studies shows an excellent agreement and verified the magnetic fields density both inside and outside the nanopore. The radially non-uniform currents resulted in highly non-uniform magnetic fields within the nanopore that decay as 1/r outside the nanopore. It is worth noting that for either streaming currents or streaming potential cases, the maximum magnetic field occurred inside the pore in the vicinity of nanopore wall, as opposed to a cylindrical conductor that carries a steady electric current where the maximum magnetic fields occur at the perimeter of conductor. Based on these results, it is suggested and envisaged that non-invasive external magnetic fields readouts generated by streaming/ionic currents may be viewed as secondary electronic signatures of biomolecules to complement and enhance current DNA nanopore sequencing techniques. PMID:27833119

A Nanoporous Alumina Membrane Based Electrochemical Biosensor for Histamine Determination with Biofunctionalized Magnetic Nanoparticles Concentration and Signal Amplification

PubMed Central

Ye, Weiwei; Xu, Yifan; Zheng, Lihao; Zhang, Yu; Yang, Mo; Sun, Peilong

2016-01-01

Histamine is an indicator of food quality and indispensable in the efficient functioning of various physiological systems. Rapid and sensitive determination of histamine is urgently needed in food analysis and clinical diagnostics. Traditional histamine detection methods require qualified personnel, need complex operation processes, and are time-consuming. In this study, a biofunctionalized nanoporous alumina membrane based electrochemical biosensor with magnetic nanoparticles (MNPs) concentration and signal amplification was developed for histamine determination. Nanoporous alumina membranes were modified by anti-histamine antibody and integrated into polydimethylsiloxane (PDMS) chambers. The specific antibody modified MNPs were used to concentrate histamine from samples and transferred to the antibody modified nanoporous membrane. The MNPs conjugated to histamine were captured in the nanopores via specific reaction between histamine and anti-histamine antibody, resulting in a blocking effect that was amplified by MNPs in the nanopores. The blockage signals could be measured by electrochemical impedance spectroscopy across the nanoporous alumina membrane. The sensing platform had great sensitivity and the limit of detection (LOD) reached as low as 3 nM. This biosensor could be successfully applied for histamine determination in saury that was stored in frozen conditions for different hours, presenting a potentially novel, sensitive, and specific sensing system for food quality assessment and safety support. PMID:27782087

Fabrication of nanoporous thin-film working electrodes and their biosensing applications.

PubMed

Li, Tingjie; Jia, Falong; Fan, Yaxi; Ding, Zhifeng; Yang, Jun

2013-04-15

Electrochemical detection for point-of-care diagnostics is of great interest due to its high sensitivity, fast analysis time and ability to operate on a small scale. Herein, we report the fabrication of a nanoporous thin-film electrode and its application in the configuration of a simple and robust enzymatic biosensor. The nanoporous thin-film was formed in a planar gold electrode through an alloying/dealloying process. The nanoporous electrode has an electroactive surface area up to 40 times higher than that of a flat gold electrode of the same size. The nanoporous electrode was used as a substrate to build an enzymatic electrochemical biosensor for the detection of glucose in standard samples and control serum samples. The example glucose biosensor has a linear response up to 30 mM, with a high sensitivity of 0.50 μA mM⁻¹ mm⁻², and excellent anti-interference ability against lactate, uric acid and ascorbic acid. Abundant catalyst and enzyme were stably entrapped in the nanoporous structure, leading to high stability and reproducibility of the biosensor. Development of such nanoporous structure enables the miniaturization of high-performance electrochemical biosensors for point-of-care diagnostics or environmental field testing. Copyright © 2012 Elsevier B.V. All rights reserved.

Negative differential electrolyte resistance in a solid-state nanopore resulting from electroosmotic flow bistability.

PubMed

Luo, Long; Holden, Deric A; White, Henry S

2014-03-25

A solid-state nanopore separating two aqueous solutions containing different concentrations of KCl is demonstrated to exhibit negative differential resistance (NDR) when a constant pressure is applied across the nanopore. NDR refers to a decrease in electrical current when the voltage applied across the nanopore is increased. NDR results from the interdependence of solution flow (electroosmotic and pressure-engendered) with the distributions of K+ and Cl- within the nanopore. A switch from a high-conductivity state to a low-conductivity state occurs over a very narrow voltage window (<2 mV) that depends on the nanopore geometry, electrolyte concentration, and nanopore surface charge density. Finite element simulations based on a simultaneous solution of the Navier-Stokes, Poisson, and Nernst-Planck equations demonstrate that NDR results from a positive feedback mechanism between the ion distributions and electroosmotic flow, yielding a true bistability in fluid flow and electrical current at a critical applied voltage, i.e., the NDR "switching potential". Solution pH and Ca2+ were separately employed as chemical stimuli to investigate the dependence of the NDR on the surface charge density. The NDR switching potential is remarkably sensitive to the surface charge density, and thus to pH and the presence of Ca2+, suggesting possible applications in chemical sensing.

Ion Current Rectification, Limiting and Overlimiting Conductances in Nanopores

PubMed Central

van Oeffelen, Liesbeth; Van Roy, Willem; Idrissi, Hosni; Charlier, Daniel; Lagae, Liesbet; Borghs, Gustaaf

2015-01-01

Previous reports on Poisson-Nernst-Planck (PNP) simulations of solid-state nanopores have focused on steady state behaviour under simplified boundary conditions. These are Neumann boundary conditions for the voltage at the pore walls, and in some cases also Donnan equilibrium boundary conditions for concentrations and voltages at both entrances of the nanopore. In this paper, we report time-dependent and steady state PNP simulations under less restrictive boundary conditions, including Neumann boundary conditions applied throughout the membrane relatively far away from the nanopore. We simulated ion currents through cylindrical and conical nanopores with several surface charge configurations, studying the spatial and temporal dependence of the currents contributed by each ion species. This revealed that, due to slow co-diffusion of oppositely charged ions, steady state is generally not reached in simulations or in practice. Furthermore, it is shown that ion concentration polarization is responsible for the observed limiting conductances and ion current rectification in nanopores with asymmetric surface charges or shapes. Hence, after more than a decade of collective research attempting to understand the nature of ion current rectification in solid-state nanopores, a relatively intuitive model is retrieved. Moreover, we measured and simulated current-voltage characteristics of rectifying silicon nitride nanopores presenting overlimiting conductances. The similarity between measurement and simulation shows that overlimiting conductances can result from the increased conductance of the electric double-layer at the membrane surface at the depletion side due to voltage-induced polarization charges. The MATLAB source code of the simulation software is available via the website http://micr.vub.ac.be. PMID:25978328

Nanoporous materials for reducing the over potential of creating hydrogen by water electrolysis

DOEpatents

Anderson, Marc A.; Leonard, Kevin C.

2016-06-14

Disclosed is an electrolyzer including an electrode including a nanoporous oxide-coated conducting material. Also disclosed is a method of producing a gas through electrolysis by contacting an aqueous solution with an electrode connected to an electrical power source, wherein the electrode includes a nanoporous oxide-coated conducting material.

Selectively Sized Graphene-Based Nanopores for in Situ Single Molecule Sensing

PubMed Central

2015-01-01

The use of nanopore biosensors is set to be extremely important in developing precise single molecule detectors and providing highly sensitive advanced analysis of biological molecules. The precise tailoring of nanopore size is a significant step toward achieving this, as it would allow for a nanopore to be tuned to a corresponding analyte. The work presented here details a methodology for selectively opening nanopores in real-time. The tunable nanopores on a quartz nanopipette platform are fabricated using the electroetching of a graphene-based membrane constructed from individual graphene nanoflakes (ø ∼30 nm). The device design allows for in situ opening of the graphene membrane, from fully closed to fully opened (ø ∼25 nm), a feature that has yet to be reported in the literature. The translocation of DNA is studied as the pore size is varied, allowing for subfeatures of DNA to be detected with slower DNA translocations at smaller pore sizes, and the ability to observe trends as the pore is opened. This approach opens the door to creating a device that can be target to detect specific analytes. PMID:26204996

Analysis of effect of nanoporous alumina substrate coated with polypyrrole nanowire on cell morphology based on AFM topography.

PubMed

El-Said, Waleed Ahmed; Yea, Cheol-Heon; Jung, Mi; Kim, Hyuncheol; Choi, Jeong-Woo

2010-05-01

In this study, in situ electrochemical synthesis of polypyrrole nanowires with nanoporous alumina template was described. The formation of highly ordered porous alumina substrate was demonstrated with Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). In addition, Fourier transform infrared analysis confirmed that polypyrrole (PP) nanowires were synthesized by direct electrochemical oxidation of pyrrole. HeLa cancer cells and HMCF normal cells were immobilized on the polypyrrole nanowires/nanoporous alumina substrates to determine the effects of the substrate on the cell morphology, adhesion and proliferation as well as the biocompatibility of the substrate. Cell adhesion and proliferation were characterized using a standard MTT assay. The effects of the polypyrrole nanowires/nanoporous alumina substrate on the cell morphology were studied by AFM. The nanoporous alumina coated with polypyrrole nanowires was found to exhibit better cell adhesion and proliferation than polystyrene petridish, aluminum foil, 1st anodized and uncoated 2nd anodized alumina substrate. This study showed the potential of the polypyrrole nanowires/nanoporous alumina substrate as biocompatibility electroactive polymer substrate for both healthy and cancer cell cultures applications.

ATOMIC LAYER DEPOSITION OF TITANIUM OXIDE THIN FILMS ONNANOPOROUS ALUMINA TEMPLATES FOR MEDICAL APPLICATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brigmon, R.

2009-05-05

Nanostructured materials may play a significant role in controlled release of pharmacologic agents for treatment of cancer. Many nanoporous polymer materials are inadequate for use in drug delivery. Nanoporous alumina provides several advantages over other materials for use in controlled drug delivery and other medical applications. Atomic layer deposition was used to coat all the surfaces of the nanoporous alumina membrane in order to reduce the pore size in a controlled manner. Both the 20 nm and 100 nm titanium oxide-coated nanoporous alumina membranes did not exhibit statistically lower viability compared to the uncoated nanoporous alumina membrane control materials. Inmore » addition, 20 nm pore size titanium oxide-coated nanoporous alumina membranes exposed to ultraviolet light demonstrated activity against Escherichia coli and Staphylococcus aureus bacteria. Nanostructured materials prepared using atomic layer deposition may be useful for delivering a pharmacologic agent at a precise rate to a specific location in the body. These materials may serve as the basis for 'smart' drug delivery devices, orthopedic implants, or self-sterilizing medical devices.« less

Enhanced Azo-Dyes Degradation Performance of Fe-Si-B-P Nanoporous Architecture

PubMed Central

Weng, Nan; Wang, Feng; Qin, Fengxiang; Tang, Wanying; Dan, Zhenhua

2017-01-01

Nanoporous structures were fabricated from Fe76Si9B10P5 amorphous alloy annealed at 773 K by dealloying in 0.05 M H2SO4 solution, as a result of preferential dissolution of α-Fe grains in form of the micro-coupling cells between α-Fe and cathodic residual phases. Nanoporous Fe-Si-B-P powders exhibit much better degradation performance to methyl orange and direct blue azo dyes compared with gas-atomized Fe76Si9B10P5 amorphous powders and commercial Fe powders. The degradation reaction rate constants of nanoporous powders are almost one order higher than those of the amorphous counterpart powders and Fe powders, accompanying with lower activation energies of 19.5 and 26.8 kJ mol−1 for the degradation reactions of methyl orange and direct blue azo dyes, respectively. The large surface area of the nanoporous structure, and the existence of metalloids as well as residual amorphous phase with high catalytic activity are responsible for the enhanced azo-dyes degradation performance of the nanoporous Fe-Si-B-P powders. PMID:28846622

Single molecule transistor based nanopore for the detection of nicotine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ray, S. J., E-mail: ray.sjr@gmail.com

A nanopore based detection methodology was proposed and investigated for the detection of Nicotine. This technique uses a Single Molecular Transistor working as a nanopore operational in the Coulomb Blockade regime. When the Nicotine molecule is pulled through the nanopore area surrounded by the Source(S), Drain (D), and Gate electrodes, the charge stability diagram can detect the presence of the molecule and is unique for a specific molecular structure. Due to the weak coupling between the different electrodes which is set by the nanopore size, the molecular energy states stay almost unaffected by the electrostatic environment that can be realisedmore » from the charge stability diagram. Identification of different orientation and position of the Nicotine molecule within the nanopore area can be made from specific regions of overlap between different charge states on the stability diagram that could be used as an electronic fingerprint for detection. This method could be advantageous and useful to detect the presence of Nicotine in smoke which is usually performed using chemical chromatography techniques.« less

DETECTION OF TWO ISOMERIC BINDING CONFIGURATIONS IN A PROTEIN-APTAMER COMPLEX WITH A BIOLOGICAL NANOPORE

PubMed Central

Van Meervelt, Veerle; Soskine, Misha; Maglia, Giovanni

2015-01-01

Protein-DNA interactions play critical roles in biological systems, and they often involve complex mechanisms and dynamics that are not easily measured by ensemble experiments. Recently, we have shown that folded proteins can be internalised inside ClyA nanopores and studied by ionic current recordings at the single-molecule level. Here, we use ClyA nanopores to sample the interaction between the G-quadruplex fold of the thrombin binding aptamer (TBA) and human thrombin (HT). Surprisingly, the internalisation of the HT:TBA complex inside the nanopore induced two types of current blockades with distinguished residual current and lifetime. Using single nucleobase substitutions to TBA we showed that these two types of blockades originate from TBA binding to thrombin with two isomeric orientations. Voltage dependencies and the use of ClyA nanopores with two different diameters allowed assessing the effect of the applied potential and confinement, and revealed that the two binding configurations of TBA to HT display different lifetimes. These results show that the ClyA nanopores might provide a new approach to probe conformational heterogeneity in protein:DNA interactions. PMID:25493908

Molecular Simulation Evaluation of Macromolecular Transport through Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

Almodovar Arbelo, Noelia; Boudouris, Bryan; Corti, David

A hybrid Monte Carlo and Molecular Dynamics simulation technique was implemented to elucidate the equilibrium behavior and transport properties of a model macromolecule as it navigated across a nanoporous polymer thin film (i.e., a nanofiltration membrane). The model linear homopolymer chosen was one that had interactions that were representative of poly(ethylene oxide) (PEO) due to the known interactions of PEO with solution molecules when a PEO chain is dissolved in an aqueous environment. The structural rearrangements of the PEO chain as it passes through the nanopore under an imposed chemical potential gradient was quantified as a function of solvent quality, polymer chain length, nanopore diameter and shape, and PEO-nanopore wall interactions. Thus, these computational studies provide a more detailed picture of the underlying physical mechanisms that drive macromolecular transport through nanopores, and, in particular, how dimensionally-large macromolecules (i.e., with large radii of gyration) enter and move through dimensionally-small pores (i.e., small radii nanopores). The insights gained from these studies will aid in the development of more cost-effective water purification systems in separation technologies for myriad industrial applications.

Advanced Nanoporous Materials for Micro-Gravimetric Sensing to Trace-Level Bio/Chemical Molecules

PubMed Central

Xu, Pengcheng; Li, Xinxin; Yu, Haitao; Xu, Tiegang

2014-01-01

Functionalized nanoporous materials have been developed recently as bio/chemical sensing materials. Due to the huge specific surface of the nano-materials for molecular adsorption, high hopes have been placed on gravimetric detection with micro/nano resonant cantilevers for ultra-sensitive sensing of low-concentration bio/chemical substances. In order to enhance selectivity of the gravimetric resonant sensors to the target molecules, it is crucial to modify specific groups onto the pore-surface of the nano-materials. By loading the nanoporous sensing material onto the desired region of the mass-type transducers like resonant cantilevers, the micro-gravimetric bio/chemical sensors can be formed. Recently, such micro-gravimetric bio/chemical sensors have been successfully applied for rapid or on-the-spot detection of various bio/chemical molecules at the trace-concentration level. The applicable nanoporous sensing materials include mesoporous silica, zeolite, nanoporous graphene oxide (GO) and so on. This review article focuses on the recent achievements in design, preparation, functionalization and characterization of advanced nanoporous sensing materials for micro-gravimetric bio/chemical sensing. PMID:25313499

Nanowire-nanopore transistor sensor for DNA detection during translocation

NASA Astrophysics Data System (ADS)

Xie, Ping; Xiong, Qihua; Fang, Ying; Qing, Quan; Lieber, Charles

2011-03-01

Nanopore sequencing, as a promising low cost, high throughput sequencing technique, has been proposed more than a decade ago. Due to the incompatibility between small ionic current signal and fast translocation speed and the technical difficulties on large scale integration of nanopore for direct ionic current sequencing, alternative methods rely on integrated DNA sensors have been proposed, such as using capacitive coupling or tunnelling current etc. But none of them have been experimentally demonstrated yet. Here we show that for the first time an amplified sensor signal has been experimentally recorded from a nanowire-nanopore field effect transistor sensor during DNA translocation. Independent multi-channel recording was also demonstrated for the first time. Our results suggest that the signal is from highly localized potential change caused by DNA translocation in none-balanced buffer condition. Given this method may produce larger signal for smaller nanopores, we hope our experiment can be a starting point for a new generation of nanopore sequencing devices with larger signal, higher bandwidth and large-scale multiplexing capability and finally realize the ultimate goal of low cost high throughput sequencing.

Self-ordered, controlled structure nanoporous membranes using constant current anodization.

PubMed

Lee, Kwan; Tang, Yun; Ouyang, Min

2008-12-01

We report a constant current (CC) based anodization technique to fabricate and control structure of mechanically stable anodic aluminum oxide (AAO) membranes with a long-range ordered hexagonal nanopore pattern. For the first time we show that interpore distance (Dint) of a self-ordered nanopore feature can be continuously tuned over a broad range with CC anodization and is uniquely defined by the conductivity of sulfuric acid as electrolyte. We further demonstrate that this technique can offer new degrees of freedom for engineering planar nanopore structures by fine tailoring the CC based anodization process. Our results not only facilitate further understanding of self-ordering mechanism of alumina membranes but also provide a fast, simple (without requirement of prepatterning or preoxide layer), and flexible methodology for controlling complex nanoporous structures, thus offering promising practical applications in nanotechnology.

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

PubMed

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

PubMed Central

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-01-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I–V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later. PMID:28252106

Nanopore arrays in a silicon membrane for parallel single-molecule detection: fabrication

NASA Astrophysics Data System (ADS)

Schmidt, Torsten; Zhang, Miao; Sychugov, Ilya; Roxhed, Niclas; Linnros, Jan

2015-08-01

Solid state nanopores enable translocation and detection of single bio-molecules such as DNA in buffer solutions. Here, sub-10 nm nanopore arrays in silicon membranes were fabricated by using electron-beam lithography to define etch pits and by using a subsequent electrochemical etching step. This approach effectively decouples positioning of the pores and the control of their size, where the pore size essentially results from the anodizing current and time in the etching cell. Nanopores with diameters as small as 7 nm, fully penetrating 300 nm thick membranes, were obtained. The presented fabrication scheme to form large arrays of nanopores is attractive for parallel bio-molecule sensing and DNA sequencing using optical techniques. In particular the signal-to-noise ratio is improved compared to other alternatives such as nitride membranes suffering from a high-luminescence background.

Nanopore arrays in a silicon membrane for parallel single-molecule detection: fabrication.

PubMed

Schmidt, Torsten; Zhang, Miao; Sychugov, Ilya; Roxhed, Niclas; Linnros, Jan

2015-08-07

Solid state nanopores enable translocation and detection of single bio-molecules such as DNA in buffer solutions. Here, sub-10 nm nanopore arrays in silicon membranes were fabricated by using electron-beam lithography to define etch pits and by using a subsequent electrochemical etching step. This approach effectively decouples positioning of the pores and the control of their size, where the pore size essentially results from the anodizing current and time in the etching cell. Nanopores with diameters as small as 7 nm, fully penetrating 300 nm thick membranes, were obtained. The presented fabrication scheme to form large arrays of nanopores is attractive for parallel bio-molecule sensing and DNA sequencing using optical techniques. In particular the signal-to-noise ratio is improved compared to other alternatives such as nitride membranes suffering from a high-luminescence background.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

NASA Astrophysics Data System (ADS)

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-01

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later.

Nonfaradaic nanoporous electrochemistry for conductometry at high electrolyte concentration.

PubMed

Bae, Je Hyun; Kang, Chung Mu; Choi, Hyoungseon; Kim, Beom Jin; Jang, Woohyuk; Lim, Sung Yul; Kim, Hee Chan; Chung, Taek Dong

2015-02-17

Nanoporous electrified surfaces create a unique nonfaradaic electrochemical behavior that is sensitively influenced by pore size, morphology, ionic strength, and electric field modulation. Here, we report the contributions of ion concentration and applied ac frequency to the electrode impedance through an electrical double layer overlap and ion transport along the nanopores. Nanoporous Pt with uniform pore size and geometry (L2-ePt) responded more sensitively to conductivity changes in aqueous solutions than Pt black with poor uniformity despite similar real surface areas and enabled the previously difficult quantitative conductometry measurements at high electrolyte concentrations. The nanopores of L2-ePt were more effective in reducing the electrode impedance and exhibited superior linear responses to not only flat Pt but also Pt black, leading to successful conductometric detection in ion chromatography without ion suppressors and at high ionic strengths.

Engineering of highly ordered TiO2 nanopore arrays by anodization

NASA Astrophysics Data System (ADS)

Wang, Huijie; Huang, Zhennan; Zhang, Li; Ding, Jie; Ma, Zhaoxia; Liu, Yong; Kou, Shengzhong; Yang, Hangsheng

2016-07-01

Finite element analysis was used to simulate the current density distributions in the TiO2 barrier layer formed at the initial stage of Ti anodization. The morphology modification of the barrier layer was found to induce current density distribution change. By starting the anodization with proper TiO2 barrier layer morphology, the current density distribution can be adjusted to favor the formation of either nanotube arrays or nanopore arrays of anodic TiO2. We also found that the addition of sodium acetate into the electrolyte suppressed both the field-assisted chemical dissolution of TiO2 and the TiF62- hydrolysis induced TiO2 deposition during anodization, and thus further favored the nanopore formation. Accordingly, highly ordered anodic TiO2 nanopore arrays, similar to anodic aluminum oxide nanopore arrays, were successfully prepared.

Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers.

PubMed

Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

2017-03-02

Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO 2 /nanoporous-Si and the TiO 2 /nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO 2 /nanoporous Si are lower than that of the HfO 2 /nanoporous Si, the former is more stable than the later.

Bioinspired integrated nanosystems based on solid-state nanopores: “iontronic” transduction of biological, chemical and physical stimuli

PubMed Central

Pérez-Mitta, Gonzalo; Albesa, Alberto G.; Trautmann, Christina; Toimil-Molares, María Eugenia

2017-01-01

The ability of living systems to respond to stimuli and process information has encouraged scientists to develop integrated nanosystems displaying similar functions and capabilities. In this regard, biological pores have been a source of inspiration due to their exquisite control over the transport of ions within cells, a feature that ultimately plays a major role in multiple physiological processes, e.g. transduction of physical stimuli into nervous signals. Developing abiotic nanopores, which respond to certain chemical, biological or physical inputs producing “iontronic” signals, is now a reality thanks to the combination of “soft” surface science with nanofabrication techniques. The interplay between the functional richness of predesigned molecular components and the remarkable physical characteristics of nanopores plays a critical role in the rational integration of molecular functions into nanopore environments, permitting us to envisage nanopore-based biomimetic integrated nanosystems that respond to a variety of external stimuli such as pH, redox potential, molecule concentration, temperature, or light. Transduction of these stimuli into a predefined “iontronic” response can be amplified by exploiting nanoconfinement and physico-chemical effects such as charge distribution, steric constraints, equilibria displacement, or local changes in ionic concentration, to name but a few examples. While in past decades the focus has been mostly on their fundamental aspects and the in-depth study of their interesting transport properties, for several years now nanopore research has started to shift towards specific practical applications. This work is dedicated to bringing together the latest developments in the use of nanopores as “iontronic” transducing elements. Our aim is to show the wide potential of abiotic nanopores in sensing and signal transduction and also to promote the potential of this technology among doctoral students, postdocs, and researchers. We believe that even a casual reader of this perspective will not fail to be impressed by the wealth of opportunities that solid-state nanopores can offer to the transduction of biological, physical and chemical stimuli. PMID:28572900

CO2 Photoreduction by Formate Dehydrogenase and a Ru-Complex in a Nanoporous Glass Reactor.

PubMed

Noji, Tomoyasu; Jin, Tetsuro; Nango, Mamoru; Kamiya, Nobuo; Amao, Yutaka

2017-02-01

In this study, we demonstrated the conversion of CO 2 to formic acid under ambient conditions in a photoreduction nanoporous reactor using a photosensitizer, methyl viologen (MV 2+ ), and formate dehydrogenase (FDH). The overall efficiency of this reactor was 14 times higher than that of the equivalent solution. The accumulation rate of formic acid in the nanopores of 50 nm is 83 times faster than that in the equivalent solution. Thus, this CO 2 photoreduction nanoporous glass reactor will be useful as an artificial photosynthesis system that converts CO 2 to fuel.

Nanoporous carbon actuator and methods of use thereof

DOEpatents

Biener, Juergen [San Leandro, CA; Baumann, Theodore F [Discovery Bay, CA; Shao, Lihua [Karlsruhe, DE; Weissmueller, Joerg [Stutensee, DE

2012-07-31

An electrochemically driveable actuator according to one embodiment includes a nanoporous carbon aerogel composition capable of exhibiting charge-induced reversible strain when wetted by an electrolyte and a voltage is applied thereto. An electrochemically driven actuator according to another embodiment includes a nanoporous carbon aerogel composition wetted by an electrolyte; and a mechanism for causing charge-induced reversible strain of the composition. A method for electrochemically actuating an object according to one embodiment includes causing charge-induced reversible strain of a nanoporous carbon aerogel composition wetted with an electrolyte to actuate the object by the strain.

Solvothermal synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces.

PubMed

Zhang, Yong-Lai; Wang, Jian-Nan; He, Yan; He, Yinyan; Xu, Bin-Bin; Wei, Shu; Xiao, Feng-Shou

2011-10-18

Reported here is a facile synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces. Taking this nanoporous polymer as a media, superhydrophobicity is rapidly imparted onto three typical kinds of substrates, including paper, transparent polydimethylsiloxane (PDMS), and finger skin. Quantitative characterization showed that the adhesion between the water droplet and polymer-coated substrates decreased significantly compared to that on the original surface, further indicating the effective wetting mode transformation. The nanoporous polymer coating would open a new door for facile, rapid, safe, and larger scale fabrication of superhydrophobic surfaces on general substrates. © 2011 American Chemical Society

DNA origami nanopores: developments, challenges and perspectives

NASA Astrophysics Data System (ADS)

Hernández-Ainsa, Silvia; Keyser, Ulrich F.

2014-11-01

DNA nanotechnology has enabled the construction of DNA origami nanopores; synthetic nanopores that present improved capabilities for the area of single molecule detection. Their extraordinary versatility makes them a new and powerful tool in nanobiotechnology for a wide range of important applications beyond molecular sensing. In this review, we briefly present the recent developments in this emerging field of research. We discuss the current challenges and possible solutions that would enhance the sensing capabilities of DNA origami nanopores. Finally, we anticipate novel avenues for future research and highlight a range of exciting ideas and applications that could be explored in the near future.

Pore structure and function of synthetic nanopores with fixed charges: tip shape and rectification properties

NASA Astrophysics Data System (ADS)

Ramírez, Patricio; Apel, Pavel Yu; Cervera, Javier; Mafé, Salvador

2008-08-01

We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst-Planck equations. According to our results, the nanopore transport properties, such as current-voltage (I-V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.

Pore structure and function of synthetic nanopores with fixed charges: tip shape and rectification properties.

PubMed

Ramírez, Patricio; Apel, Pavel Yu; Cervera, Javier; Mafé, Salvador

2008-08-06

We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst-Planck equations. According to our results, the nanopore transport properties, such as current-voltage (I-V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores.

PubMed

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

NASA Astrophysics Data System (ADS)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

Nanoscale Probing of Electrical Signals in Biological Systems

DTIC Science & Technology

2012-03-18

Membranes Anodized aluminum oxide ( AAO ) is an ideal prototype substrate for studying ion transport through nanoporous membranes . For optimal...electrochemical microscopy, scanning ion conductance microscopy, nanoporous membranes , anodized aluminum oxide , atomic layer deposition, focused ion beam...capacity. This approach utilizes atomic layer deposition (ALD) of a thin conformal Ir film into a nanoporous anodized aluminum oxide (

Nano/macro porous bioactive glass scaffold

NASA Astrophysics Data System (ADS)

Wang, Shaojie

Bioactive glass (BG) and ceramics have been widely studied and developed as implants to replace hard tissues of the musculo-skeletal system, such as bones and teeth. Recently, instead of using bulk materials, which usually do not degrade rapidly enough and may remain in the human body for a long time, the idea of bioscaffold for tissue regeneration has generated much interest. An ideal bioscaffold is a porous material that would not only provide a three-dimensional structure for the regeneration of natural tissue, but also degrade gradually and, eventually be replaced by the natural tissue completely. Among various material choices the nano-macro dual porous BG appears as the most promising candidate for bioscaffold applications. Here macropores facilitate tissue growth while nanopores control degradation and enhance cell response. The surface area, which controls the degradation of scaffold can also be tuned by changing the nanopore size. However, fabrication of such 3D structure with desirable nano and macro pores has remained challenging. In this dissertation, sol-gel process combined with spinodal decomposition or polymer sponge replication method has been developed to fabricate the nano-macro porous BG scaffolds. Macropores up to 100microm are created by freezing polymer induced spinodal structure through sol-gel transition, while larger macropores (>200um) of predetermined size are obtained by the polymer sponge replication technique. The size of nanopores, which are inherent to the sol-gel method of glass fabrication, has been tailored using several approaches: Before gel point, small nanopores are generated using acid catalyst that leads to weakly-branched polymer-like network. On the other hand, larger nanopores are created with the base-catalyzed gel with highly-branched cluster-like structure. After the gel point, the nanostructure can be further modified by manipulating the sintering temperature and/or the ammonia concentration used in the solvent exchange process. Although both techniques lower the surface area of BG scaffolds, the temperature-dependent sintering process closes nanopores through densification, while the concentration-dependent solvent exchange process enlarges nanopores through Ostwald-ripening type coarsening. Therefore, nanopore size and surface area of BG scaffold are independently controlled using these methods. In vitro cell and in vivo animal tissue responses have been investigated to evaluate the performance of the nano-macro porous BG scaffold. The cells are found to migrate and penetrate deep into the 3D nano-macro porous structure, while exhibiting excellent adhesion to the bioscaffold surface. Importantly, the new tissue with both blood vessels and collagen fibers is formed deep inside the implanted scaffolds without obvious inflammatory reaction. Furthermore, our observations show biological benefits of the nanopores in the BG scaffold. In comparison to BG scaffold without nanopores, cells migrate and penetrate into nano-macro dual-porous BG scaffold faster and deeper mainly because of the increase of surface area. To study the effect of nanopore topography, we fabricated BG scaffolds with the same surface area but different nanopore sizes. It is found that the initial cell attachment is significantly enhanced on the BG scaffold with the same surface area but smaller nanopores size, indicating that the nanopore topography strongly influences the performance of BG scaffold. In conclusion, the present results demonstrate most clearly the usefulness of our nano-macro dual-porous BG as a novel and superior 3D bioscaffold for regenerative medicine and hard tissue engineering.

DNA Sequence-Dependent Ionic Currents in Ultra-Small Solid-State Nanopores†

PubMed Central

Comer, Jeffrey

2016-01-01

Measurements of ionic currents through nanopores partially blocked by DNA have emerged as a powerful method for characterization of the DNA nucleotide sequence. Although the effect of the nucleotide sequence on the nanopore blockade current has been experimentally demonstrated, prediction and interpretation of such measurements remain a formidable challenge. Using atomic resolution computational approaches, here we show how the sequence, molecular conformation, and pore geometry affect the blockade ionic current in model solid-state nanopores. We demonstrate that the blockade current from a DNA molecule is determined by the chemical identities and conformations of at least three consecutive nucleotides. We find the blockade currents produced by the nucleotide triplets to vary considerably with their nucleotide sequence despite having nearly identical molecular conformations. Encouragingly, we find blockade current differences as large as 25% for single-base substitutions in ultra small (1.6 nm × 1.1 nm cross section; 2 nm length) solid-state nanopores. Despite the complex dependence of the blockade current on the sequence and conformation of the DNA triplets, we find that, under many conditions, the number of thymine bases is positively correlated with the current, whereas the number of purine bases and the presence of both purine and pyrimidines in the triplet are negatively correlated with the current. Based on these observations, we construct a simple theoretical model that relates the ion current to the base content of a solid-state nanopore. Furthermore, we show that compact conformations of DNA in narrow pores provide the greatest signal-to-noise ratio for single base detection, whereas reduction of the nanopore length increases the ionic current noise. Thus, the sequence dependence of nanopore blockade current can be theoretically rationalized, although the predictions will likely need to be customized for each nanopore type. PMID:27103233

Nanopores creation in boron and nitrogen doped polycrystalline graphene: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Izadifar, Mohammadreza; Abadi, Rouzbeh; Nezhad Shirazi, Ali Hossein; Alajlan, Naif; Rabczuk, Timon

2018-05-01

In the present paper, molecular dynamic simulations have been conducted to investigate the nanopores creation on 10% of boron and nitrogen doped polycrystalline graphene by silicon and diamond nanoclusters. Two types of nanoclusters based on silicon and diamond are used to investigate their effect for the fabrication of nanopores. Therefore, three different diameter sizes of the clusters with five kinetic energies of 10, 50, 100, 300 and 500 eV/atom at four different locations in boron or nitrogen doped polycrystalline graphene nanosheets have been perused. We also study the effect of 3% and 6% of boron doped polycrystalline graphene with the best outcome from 10% of doping. Our results reveal that the diamond cluster with diameter of 2 and 2.5 nm fabricates the largest nanopore areas on boron and nitrogen doped polycrystalline graphene, respectively. Furthermore, the kinetic energies of 10 and 50 eV/atom can not fabricate nanopores in some cases for silicon and diamond clusters on boron doped polycrystalline graphene nanosheets. On the other hand, silicon and diamond clusters fabricate nanopores for all locations and all tested energies on nitrogen doped polycrystalline graphene. The area sizes of nanopores fabricated by silicon and diamond clusters with diameter of 2 and 2.5 nm are close to the actual area size of the related clusters for the kinetic energy of 300 eV/atom in all locations on boron doped polycrystalline graphene. The maximum area and the average maximum area of nanopores are fabricated by the kinetic energy of 500 eV/atom inside the grain boundary at the center of the nanosheet and in the corner of nanosheet with diameters of 2 and 3 nm for silicon and diamond clusters on boron and nitrogen doped polycrystalline graphene.

Biodegradable hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol), poly(ethylene glycol), and polycaprolactone as in situ thermogels.

PubMed

Li, Zibiao; Zhang, Zhongxing; Liu, Kerh Li; Ni, Xiping; Li, Jun

2012-12-10

This paper reports the synthesis and characterization of new hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), and polycaprolactone (PCL) segments as in situ thermogels. The hyperbranched poly(PPG/PEG/PCL urethane)s, termed as HBPEC copolymers, were synthesized from PPG-diol, PEG-diol, and PCL-triol by using 1,6-hexamethylene diisocyanate (HMDI) as a coupling agent. The compositions and structures of HBPEC copolymers were determined by GPC and 1H NMR spectroscopy. We carried out comparative studies of the new hyperbranched copolymers with their linear counterparts, the linear poly(PPG/PEG/PCL urethane) (LPEC) copolymer and Pluronic F127 PEG-PPG-PEG block copolymer, in terms of their self-assembly and aggregation behaviors and thermoresponsive properties. HBPEC copolymers were found to show thermoresponsive micelle formation and aggregation behaviors. Particularly, the lower critical solution temperature (LCST) of the copolymers was significantly affected by the copolymer architecture. HBPEC copolymers showed much lower LCST than LPEC, the linear counterpart. Our studies revealed that the effect of hyperbranch architecture was more prominent in the gelation of the copolymers. The aqueous solutions of HBPEC copolymers exhibited thermogelling behaviors at critical gelation concentrations (CGCs) ranging from 4.3 to 7.4 wt %. These values are much lower than those reported on other PCL-contained linear thermogelling copolymers and Pluronic F127 copolymer. In addition, the CGC of HBPEC copolymers is much lower than the control LPEC copolymer. More interestingly, at high temperatures, while LPEC and other linear thermogelling copolymers formed turbid sol, HBPEC formed a dehydrated gel. Our data suggest that these phenomena are caused by the hyperbranched structure of HBPEC copolymers, which could increase the interaction of copolymer branches and enhance the chain association through synergetic hydrogen bonding effect. The thermogelling behavior of HBPEC block copolymers was further evidenced by the 1H NMR molecular dynamic study and rheological study, which further support the above hypothesis. The hydrolytic degradation study showed that the HBPEC copolymer hydrogels are biodegradable under physiological conditions. Together with the good cell biocompatibility demonstrated by the cytotoxicity study, the new thermogelling copolymers reported in this paper could potentially be used as in situ-forming hydrogels for biomedical applications.

Molecular simulations for energy, environmental and pharmaceutical applications of nanoporous materials: from zeolites, metal-organic frameworks to protein crystals.

PubMed

Jiang, Jianwen; Babarao, Ravichandar; Hu, Zhongqiao

2011-07-01

Nanoporous materials have widespread applications in chemical industry, but the pathway from laboratory synthesis and testing to practical utilization of nanoporous materials is substantially challenging and requires fundamental understanding from the bottom up. With ever-growing computational resources, molecular simulations have become an indispensable tool for material characterization, screening and design. This tutorial review summarizes the recent simulation studies in zeolites, metal-organic frameworks and protein crystals, and provides a molecular overview for energy, environmental and pharmaceutical applications of nanoporous materials with increasing degree of complexity in building blocks. It is demonstrated that molecular-level studies can bridge the gap between physical and engineering sciences, unravel microscopic insights that are otherwise experimentally inaccessible, and assist in the rational design of new materials. The review is concluded with major challenges in future simulation exploration of novel nanoporous materials for emerging applications.

Scan-rate-dependent current rectification of cone-shaped silica nanopores in quartz nanopipettes.

PubMed

Guerrette, Joshua P; Zhang, Bo

2010-12-08

Here we report the voltammetric behavior of cone-shaped silica nanopores in quartz nanopipettes in aqueous solutions as a function of the scan rate, v. Current rectification behavior for silica nanopores with diameters in the range 4-25 nm was studied. The rectification behavior was found to be strongly dependent on the scan rate. At low scan rates (e.g., v < 1 V/s), the rectification ratio was found to be at its maximum and relatively independent of v. At high scan rates (e.g., v > 200 V/s), a nearly linear current-voltage response was obtained. In addition, the initial voltage was shown to play a critical role in the current-voltage response of cone-shaped nanopores at high scan rates. We explain this v-dependent current-voltage response by ionic redistribution in the vicinity of the nanopore mouth.

Interconnected V2O5 nanoporous network for high-performance supercapacitors.

PubMed

Saravanakumar, B; Purushothaman, Kamatchi K; Muralidharan, G

2012-09-26

Vanadium pentoxide (V(2)O(5)) has attracted attention for supercapcitor applications because of its extensive multifunctional properties. In the present study, V(2)O(5) nanoporous network was synthesized via simple capping-agent-assisted precipitation technique and it is further annealed at different temperatures. The effect of annealing temperature on the morphology, electrochemical and structural properties, and stability upon oxidation-reduction cycling has been analyzed for supercapacitor application. We achieved highest specific capacitance of 316 F g(-1) for interconnected V(2)O(5) nanoporous network. This interconnected nanoporous network creates facile nanochannels for ion diffusion and facilitates the easy accessibility of ions. Moreover, after six hundred consecutive cycling processes the specific capacitance has changed only by 24%. A simple cost-effective preparation technique of V(2)O(5) nanoporous network with excellent capacitive behavior, energy density, and stability encourages its possible commercial exploitation for the development of high-performance supercapacitors.

Enhanced translocation of single DNA molecules through α-hemolysin nanopores by manipulation of internal charge

PubMed Central

Maglia, Giovanni; Restrepo, Marcela Rincon; Mikhailova, Ellina; Bayley, Hagan

2008-01-01

Both protein and solid-state nanopores are under intense investigation for the analysis of nucleic acids. A crucial advantage of protein nanopores is that site-directed mutagenesis permits precise tuning of their properties. Here, by augmenting the internal positive charge within the α-hemolysin pore and varying its distribution, we increase the frequency of translocation of a 92-nt single-stranded DNA through the pore at +120 mV by ≈10-fold over the wild-type protein and dramatically lower the voltage threshold at which translocation occurs, e.g., by 50 mV for 1 event·s−1·μM−1. Further, events in which DNA enters the pore, but is not immediately translocated, are almost eliminated. These experiments provide a basis for improved nucleic acid analysis with protein nanopores, which might be translated to solid-state nanopores by using chemical surface modification. PMID:19060213

Electrochemistry at Edge of Single Graphene Layer in a Nanopore

PubMed Central

Banerjee, Shouvik; Shim, Jiwook; Rivera, Jose; Jin, Xiaozhong; Estrada, David; Solovyeva, Vita; You, Xiuque; Pak, James; Pop, Eric; Aluru, Narayana; Bashir, Rashid

2013-01-01

We study the electrochemistry of single layer graphene edges using a nanopore-based structure consisting of stacked graphene and Al2O3 dielectric layers. Nanopores, with diameters ranging from 5 to 20 nm, are formed by an electron beam sculpting process on the stacked layers. This leads to unique edge structure which, along with the atomically thin nature of the embedded graphene electrode, demonstrates electrochemical current densities as high as 1.2 × 104 A/cm2. The graphene edge embedded structure offers a unique capability to study the electrochemical exchange at an individual graphene edge, isolated from the basal plane electrochemical activity. We also report ionic current modulation in the nanopore by biasing the embedded graphene terminal with respect to the electrodes in the fluid. The high electrochemical specific current density for a graphene nanopore-based device can have many applications in sensitive chemical and biological sensing, and energy storage devices. PMID:23249127

Water desalination with a single-layer MoS2 nanopore

PubMed Central

Heiranian, Mohammad; Farimani, Amir Barati; Aluru, Narayana R.

2015-01-01

Efficient desalination of water continues to be a problem facing the society. Advances in nanotechnology have led to the development of a variety of nanoporous membranes for water purification. Here we show, by performing molecular dynamics simulations, that a nanopore in a single-layer molybdenum disulfide can effectively reject ions and allow transport of water at a high rate. More than 88% of ions are rejected by membranes having pore areas ranging from 20 to 60 Å2. Water flux is found to be two to five orders of magnitude greater than that of other known nanoporous membranes. Pore chemistry is shown to play a significant role in modulating the water flux. Pores with only molybdenum atoms on their edges lead to higher fluxes, which are ∼70% greater than that of graphene nanopores. These observations are explained by permeation coefficients, energy barriers, water density and velocity distributions in the pores. PMID:26465062

Water desalination with a single-layer MoS2 nanopore

NASA Astrophysics Data System (ADS)

Heiranian, Mohammad; Farimani, Amir Barati; Aluru, Narayana R.

2015-10-01

Efficient desalination of water continues to be a problem facing the society. Advances in nanotechnology have led to the development of a variety of nanoporous membranes for water purification. Here we show, by performing molecular dynamics simulations, that a nanopore in a single-layer molybdenum disulfide can effectively reject ions and allow transport of water at a high rate. More than 88% of ions are rejected by membranes having pore areas ranging from 20 to 60 Å2. Water flux is found to be two to five orders of magnitude greater than that of other known nanoporous membranes. Pore chemistry is shown to play a significant role in modulating the water flux. Pores with only molybdenum atoms on their edges lead to higher fluxes, which are ~70% greater than that of graphene nanopores. These observations are explained by permeation coefficients, energy barriers, water density and velocity distributions in the pores.

Water desalination with a single-layer MoS2 nanopore.

PubMed

Heiranian, Mohammad; Farimani, Amir Barati; Aluru, Narayana R

2015-10-14

Efficient desalination of water continues to be a problem facing the society. Advances in nanotechnology have led to the development of a variety of nanoporous membranes for water purification. Here we show, by performing molecular dynamics simulations, that a nanopore in a single-layer molybdenum disulfide can effectively reject ions and allow transport of water at a high rate. More than 88% of ions are rejected by membranes having pore areas ranging from 20 to 60 Å(2). Water flux is found to be two to five orders of magnitude greater than that of other known nanoporous membranes. Pore chemistry is shown to play a significant role in modulating the water flux. Pores with only molybdenum atoms on their edges lead to higher fluxes, which are ∼ 70% greater than that of graphene nanopores. These observations are explained by permeation coefficients, energy barriers, water density and velocity distributions in the pores.

Nanopore sensing at ultra-low concentrations using single-molecule dielectrophoretic trapping

NASA Astrophysics Data System (ADS)

Freedman, Kevin J.; Otto, Lauren M.; Ivanov, Aleksandar P.; Barik, Avijit; Oh, Sang-Hyun; Edel, Joshua B.

2016-01-01

Single-molecule techniques are being developed with the exciting prospect of revolutionizing the healthcare industry by generating vast amounts of genetic and proteomic data. One exceptionally promising route is in the use of nanopore sensors. However, a well-known complexity is that detection and capture is predominantly diffusion limited. This problem is compounded when taking into account the capture volume of a nanopore, typically 108-1010 times smaller than the sample volume. To rectify this disproportionate ratio, we demonstrate a simple, yet powerful, method based on coupling single-molecule dielectrophoretic trapping to nanopore sensing. We show that DNA can be captured from a controllable, but typically much larger, volume and concentrated at the tip of a metallic nanopore. This enables the detection of single molecules at concentrations as low as 5 fM, which is approximately a 103 reduction in the limit of detection compared with existing methods, while still maintaining efficient throughput.

Nanoporous carbon tunable resistor/transistor and methods of production thereof

DOEpatents

Biener, Juergen; Baumann, Theodore F; Dasgupta, Subho; Hahn, Horst

2014-04-22

In one embodiment, a tunable resistor/transistor includes a porous material that is electrically coupled between a source electrode and a drain electrode, wherein the porous material acts as an active channel, an electrolyte solution saturating the active channel, the electrolyte solution being adapted for altering an electrical resistance of the active channel based on an applied electrochemical potential, wherein the active channel comprises nanoporous carbon arranged in a three-dimensional structure. In another embodiment, a method for forming the tunable resistor/transistor includes forming a source electrode, forming a drain electrode, and forming a monolithic nanoporous carbon material that acts as an active channel and selectively couples the source electrode to the drain electrode electrically. In any embodiment, the electrolyte solution saturating the nanoporous carbon active channel is adapted for altering an electrical resistance of the nanoporous carbon active channel based on an applied electrochemical potential.

Enhanced light output from the nano-patterned InP semiconductor substrate through the nanoporous alumina mask.

PubMed

Jung, Mi; Kim, Jae Hun; Lee, Seok; Jang, Byung Jin; Lee, Woo Young; Oh, Yoo-Mi; Park, Sun-Woo; Woo, Deokha

2012-07-01

A significant enhancement in the light output from nano-patterned InP substrate covered with a nanoporous alumina mask was observed. A uniform nanohole array on an InP semiconductor substrate was fabricated by inductively coupled plasma reactive ion etching (ICP-RIE), using the nanoporous alumina mask as a shadow mask. The light output property of the semiconductor substrate was investigated via photoluminescence (PL) intensity measurement. The InP substrate with a nanohole array showed a more enhanced PL intensity compared with the raw InP substrate without a nanohole structure. After ICP-RIE etching, the light output from the nanoporous InP substrate covered with a nanoporous alumina mask showed fourfold enhanced PL intensity compared with the raw InP substrate. These results can be used as a prospective method for increasing the light output efficiency of optoelectronic devices.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

DOEpatents

Sansinena, Jose-Maria [Los Alamos, NM; Redondo, Antonio [Los Alamos, NM; Olazabal, Virginia [Los Alamos, NM; Hoffbauer, Mark A [Los Alamos, NM; Akhadov, Elshan A [Los Alamos, NM

2009-12-29

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

2017-09-12

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

2017-07-18

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Electrochemical detection of single molecules using abiotic nanopores having electrically tunable dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sansinena, Jose-Maria; Redondo, Antonio; Olazabal, Virginia

A barrier structure for use in an electrochemical stochastic membrane sensor for single molecule detection. The sensor is based upon inorganic nanopores having electrically tunable dimensions. The inorganic nanopores are formed from inorganic materials and an electrically conductive polymer. Methods of making the barrier structure and sensing single molecules using the barrier structure are also described.

Nanoscale dynamics of Joule heating and bubble nucleation in a solid-state nanopore.

PubMed

Levine, Edlyn V; Burns, Michael M; Golovchenko, Jene A

2016-01-01

We present a mathematical model for Joule heating of an electrolytic solution in a nanopore. The model couples the electrical and thermal dynamics responsible for rapid and extreme superheating of the electrolyte within the nanopore. The model is implemented numerically with a finite element calculation, yielding a time and spatially resolved temperature distribution in the nanopore region. Temperatures near the thermodynamic limit of superheat are predicted to be attained just before the explosive nucleation of a vapor bubble is observed experimentally. Knowledge of this temperature distribution enables the evaluation of related phenomena including bubble nucleation kinetics, relaxation oscillation, and bubble dynamics.

A disruptive sequencer meets disruptive publishing.

PubMed

Loman, Nick; Goodwin, Sarah; Jansen, Hans; Loose, Matt

2015-01-01

Nanopore sequencing was recently made available to users in the form of the Oxford Nanopore MinION. Released to users through an early access programme, the MinION is made unique by its tiny form factor and ability to generate very long sequences from single DNA molecules. The platform is undergoing rapid evolution with three distinct nanopore types and five updates to library preparation chemistry in the last 18 months. To keep pace with the rapid evolution of this sequencing platform, and to provide a space where new analysis methods can be openly discussed, we present a new F1000Research channel devoted to updates to and analysis of nanopore sequence data.

Buckling Causes Nonlinear Dynamics of Filamentous Viruses Driven through Nanopores.

PubMed

McMullen, Angus; de Haan, Hendrick W; Tang, Jay X; Stein, Derek

2018-02-16

Measurements and Langevin dynamics simulations of filamentous viruses driven through solid-state nanopores reveal a superlinear rise in the translocation velocity with driving force. The mobility also scales with the length of the virus in a nontrivial way that depends on the force. These dynamics are consequences of the buckling of the leading portion of a virus as it emerges from the nanopore and is put under compressive stress by the viscous forces it encounters. The leading tip of a buckled virus stalls and this reduces the total viscous drag force. We present a scaling theory that connects the solid mechanics to the nonlinear dynamics of polyelectrolytes translocating nanopores.

Top-down solid-phase fabrication of nanoporous cadmium oxide architectures.

PubMed

Yu, Haidong; Wang, Deshen; Han, Ming-Yong

2007-02-28

In this article, we have demonstrated one-step solid-phase transformation from high-quality cadmium carbonate microcrystals into highly nanoporous cadmium oxide. The high crystal quality of cadmium carbonate is critical for the successful fabrication of porous nanoarchitectures with predetermined morphology and well-controlled internal structure. This novel strategy has a good potential to prepare nanoporous materials at a large scale by using perfect monolithic carbonate crystals, and it is also useful to synthesize different nanoporous materials on metal-oxide-coated substrates. Meanwhile, this simple thermal transformation of cadmium carbonate into porous structures has further been extended to convert calcium carbonate into such porous structures.

Buckling Causes Nonlinear Dynamics of Filamentous Viruses Driven through Nanopores

NASA Astrophysics Data System (ADS)

McMullen, Angus; de Haan, Hendrick W.; Tang, Jay X.; Stein, Derek

2018-02-01

Measurements and Langevin dynamics simulations of filamentous viruses driven through solid-state nanopores reveal a superlinear rise in the translocation velocity with driving force. The mobility also scales with the length of the virus in a nontrivial way that depends on the force. These dynamics are consequences of the buckling of the leading portion of a virus as it emerges from the nanopore and is put under compressive stress by the viscous forces it encounters. The leading tip of a buckled virus stalls and this reduces the total viscous drag force. We present a scaling theory that connects the solid mechanics to the nonlinear dynamics of polyelectrolytes translocating nanopores.

Embedded CMOS basecalling for nanopore DNA sequencing.

PubMed

Chengjie Wang; Junli Zheng; Magierowski, Sebastian; Ghafar-Zadeh, Ebrahim

2016-08-01

DNA sequencing based on nanopore sensors is now entering the marketplace. The ability to interface this technology to established CMOS microelectronics promises significant improvements in functionality and miniaturization. Among the key functions to benefit from this interface will be basecalling, the conversion of raw electronic molecular signatures to nucleotide sequence predictions. This paper presents the design and performance potential of custom CMOS base-callers embedded alongside nanopore sensors. A basecalliing architecture implemented in 32-nm technology is discussed with the ability to process the equivalent of 20 human genomes per day in real-time at a power density of 5 W/cm2 assuming a 3-mer nanopore sensor.

Polymer-modified opal nanopores.

PubMed

Schepelina, Olga; Zharov, Ilya

2006-12-05

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.

Slow DNA Transport through Nanopores in Hafnium Oxide Membranes

PubMed Central

Bell, David C.; Cohen-Karni, Tzahi; Rosenstein, Jacob K.; Wanunu, Meni

2016-01-01

We present a study of double- and single-stranded DNA transport through nanopores fabricated in ultrathin (2–7 nm thick) free-standing hafnium oxide (HfO2) membranes. The high chemical stability of ultrathin HfO2 enables long-lived experiments with <2 nm diameter pores that last several hours, in which we observe >50 000 DNA translocations with no detectable pore expansion. Mean DNA velocities are slower than velocities through comparable silicon nitride pores, providing evidence that HfO2 nanopores have favorable physicochemical interactions with nucleic acids that can be leveraged to slow down DNA in a nanopore. PMID:24083444

Leakage conduction behavior in electron-beam-cured nanoporous silicate films

NASA Astrophysics Data System (ADS)

Liu, Po-Tsun; Tsai, T. M.; Chang, T. C.

2005-05-01

This letter explores the application of electron-beam curing on nanoporous silicate films. The electrical conduction mechanism for the nanoporous silicate film cured by electron-beam radiation has been studied with metal-insulator-semiconductor capacitors. Electrical analyses over a varying temperature range from room temperature to 150°C provide evidence for space-charge-limited conduction in the electron-beam-cured thin film, while Schottky-emission-type leaky behavior is seen in the counterpart typically cured by a thermal furnace. A physical model consistent with electrical analyses is also proposed to deduce the origin of conduction behavior in the nanoporous silicate thin film.

Methods And Devices For Characterizing Duplex Nucleic Acid Molecules

DOEpatents

Akeson, Mark; Vercoutere, Wenonah; Haussler, David; Winters-Hilt, Stephen

2005-08-30

Methods and devices are provided for characterizing a duplex nucleic acid, e.g., a duplex DNA molecule. In the subject methods, a fluid conducting medium that includes a duplex nucleic acid molecule is contacted with a nanopore under the influence of an applied electric field and the resulting changes in current through the nanopore caused by the duplex nucleic acid molecule are monitored. The observed changes in current through the nanopore are then employed as a set of data values to characterize the duplex nucleic acid, where the set of data values may be employed in raw form or manipulated, e.g., into a current blockade profile. Also provided are nanopore devices for practicing the subject methods, where the subject nanopore devices are characterized by the presence of an algorithm which directs a processing means to employ monitored changes in current through a nanopore to characterize a duplex nucleic acid molecule responsible for the current changes. The subject methods and devices find use in a variety of applications, including, among other applications, the identification of an analyte duplex DNA molecule in a sample, the specific base sequence at a single nulceotide polymorphism (SNP), and the sequencing of duplex DNA molecules.

Synthesis of nanoporous TiO2 materials using a doubly surfactant system and applying them as useful adsorbents

NASA Astrophysics Data System (ADS)

Anbia, Mansoor; Khosravi, Faezeh

Hydrothermal and non-hydrothermal nanoporous TiO2 materials were synthesized via a doubly surfactant route by using cationic cetyltrimethylammonium bromide and anionic sodium dodecyl sulfate surfactants as the molecular template/structure directing agent. Hydrothermal treatment was performed for comparison. The bulk chemical and phase compositions, crystalline structures, particle morphologies, thermal stabilities and surface texturing were determined by means of X-ray powder analysis, SEM and N2 sorptiometry. The nanoporous TiO2 materials were found to have a spherical morphology with a diameter range of 50-200 nm and a high surface area (390 m2 g-1). Hydrothermal and non-hydrothermal nanoporous TiO2 materials were applied for adsorption of heavy metal cations and the toxic organic compound, copper phthalocyanine, from water for evaluation of their adsorption properties. Both nanoporous TiO2 materials were found to have similar adsorption capacities toward heavy metal cations and CuPc. Both hydrothermal and non-hydrothermal TiO2 nanoporous materials were found to have very good potential for application as a new adsorbent especially for adsorbing heavy metal cations from wastewaters.

Nanotopography Promotes Pancreatic Differentiation of Human Embryonic Stem Cells and Induced Pluripotent Stem Cells.

PubMed

Kim, Jong Hyun; Kim, Hyung Woo; Cha, Kyoung Je; Han, Jiyou; Jang, Yu Jin; Kim, Dong Sung; Kim, Jong-Hoon

2016-03-22

Although previous studies suggest that nanotopographical features influence properties and behaviors of stem cells, only a few studies have attempted to derive clinically useful somatic cells from human pluripotent stem cells using nanopatterned surfaces. In the present study, we report that polystyrene nanopore-patterned surfaces significantly promote the pancreatic differentiation of human embryonic and induced pluripotent stem cells. We compared different diameters of nanopores and showed that 200 nm nanopore-patterned surfaces highly upregulated the expression of PDX1, a critical transcription factor for pancreatic development, leading to an approximately 3-fold increase in the percentage of differentiating PDX1(+) pancreatic progenitors compared with control flat surfaces. Furthermore, in the presence of biochemical factors, 200 nm nanopore-patterned surfaces profoundly enhanced the derivation of pancreatic endocrine cells producing insulin, glucagon, or somatostatin. We also demonstrate that nanopore-patterned surface-induced upregulation of PDX1 is associated with downregulation of TAZ, suggesting the potential role of TAZ in nanopore-patterned surface-mediated mechanotransduction. Our study suggests that appropriate cytokine treatments combined with nanotopographical stimulation could be a powerful tool for deriving a high purity of desired cells from human pluripotent stem cells.

Nanoporous Pirani sensor based on anodic aluminum oxide

NASA Astrophysics Data System (ADS)

Jeon, Gwang-Jae; Kim, Woo Young; Shim, Hyun Bin; Lee, Hee Chul

2016-09-01

A nanoporous Pirani sensor based on anodic aluminum oxide (AAO) is proposed, and the quantitative relationship between the performance of the sensor and the porosity of the AAO membrane is characterized with a theoretical model. The proposed Pirani sensor is composed of a metallic resistor on a suspended nanoporous membrane, which simultaneously serves as the sensing area and the supporting structure. The AAO membrane has numerous vertically-tufted nanopores, resulting in a lower measurable pressure limit due to both the increased effective sensing area and the decreased effective thermal loss through the supporting structure. Additionally, the suspended AAO membrane structure, with its outer periphery anchored to the substrate, known as a closed-type design, is demonstrated using nanopores of AAO as an etch hole without a bulk micromachining process used on the substrate. In a CMOS-compatible process, a 200 μm × 200 μm nanoporous Pirani sensor with porosity of 25% was capable of measuring the pressure from 0.1 mTorr to 760 Torr. With adjustment of the porosity of the AAO, the measurable range could be extended toward lower pressures of more than one decade compared to a non-porous membrane with an identical footprint.

Photochemistry of nanoporous carbons: Perspectives in energy conversion and environmental remediation.

PubMed

Gomis-Berenguer, Alicia; Velasco, Leticia F; Velo-Gala, Inmaculada; Ania, Conchi O

2017-03-15

The interest in the use of nanoporous carbon materials in applications related to energy conversion and storage, either as catalysts or additives, has grown over recent decades in various disciplines. Since the early studies reporting the benefits of the use of nanoporous carbons as inert supports of semiconductors and as electron acceptors that enhance the splitting of the photogenerated excitons, many researchers have investigated the key role of carbon matrices coupled to all types of photoactive materials. More recently, our group has demonstrated the ability of semiconductor-free nanoporous carbons to convert the absorbed photons into chemical reactions (i.e. oxidation of pollutants, water splitting, reduction of surface groups) opening new opportunities beyond conventional applications in light energy conversion. The aim of this paper is to review the recent progress on the application of nanoporous carbons in photochemistry using varied illumination conditions (UV, simulated solar light) and covering their role as additives to semiconductors as well as their use as photocatalysts in various fields, describing the photochemical quantum yield of nanoporous carbons for different reactions, and discussing the mechanisms postulated for the carbon/light interactions in confined pore spaces. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Ionic transport through sub-10 nm diameter hydrophobic high-aspect ratio nanopores: experiment, theory and simulation

PubMed Central

Balme, Sébastien; Picaud, Fabien; Manghi, Manoel; Palmeri, John; Bechelany, Mikhael; Cabello-Aguilar, Simon; Abou-Chaaya, Adib; Miele, Philippe; Balanzat, Emmanuel; Janot, Jean Marc

2015-01-01

Fundamental understanding of ionic transport at the nanoscale is essential for developing biosensors based on nanopore technology and new generation high-performance nanofiltration membranes for separation and purification applications. We study here ionic transport through single putatively neutral hydrophobic nanopores with high aspect ratio (of length L = 6 μm with diameters ranging from 1 to 10 nm) and with a well controlled cylindrical geometry. We develop a detailed hybrid mesoscopic theoretical approach for the electrolyte conductivity inside nanopores, which considers explicitly ion advection by electro-osmotic flow and possible flow slip at the pore surface. By fitting the experimental conductance data we show that for nanopore diameters greater than 4 nm a constant weak surface charge density of about 10−2 C m−2 needs to be incorporated in the model to account for conductance plateaus of a few pico-siemens at low salt concentrations. For tighter nanopores, our analysis leads to a higher surface charge density, which can be attributed to a modification of ion solvation structure close to the pore surface, as observed in the molecular dynamics simulations we performed. PMID:26036687

Impact of nanosecond pulsed electric fields on primary hippocampal neurons

NASA Astrophysics Data System (ADS)

Roth, Caleb C.; Payne, Jason A.; Kuipers, Marjorie A.; Thompson, Gary L.; Wilmink, Gerald J.; Ibey, Bennett L.

2012-02-01

Cellular exposure to nanosecond pulsed electric fields (nsPEF) are believed to cause immediate creation of nanopores in the plasma membrane. These nanopores enable passage of small ions, but remain impermeable to larger molecules like propidium iodide. Previous work has shown that nanopores are stable for minutes after exposure, suggesting that formation of nanopores in excitable cells could lead to prolonged action potential inhibition. Previously, we measured the formation of nanopores in neuroblastoma cells by measuring the influx of extracellular calcium by preloading cells with Calcium Green-AM. In this work, we explored the impact of changing the width of a single nsPEF, at constant amplitude, on uptake of extracellular calcium ions by primary hippocampal neurons (PHN). Calcium Green was again used to measure the influx of extracellular calcium and FM1-43 was used to monitor changes in membrane conformation. The observed thresholds for nanopore formation in PHN by nsPEF were comparable to those measured in neuroblastoma. This work is the first study of nsPEF effects on PHN and strongly suggests that neurological inhibition by nanosecond electrical pulses is highly likely at doses well below irreversible damage.

Instrumentation for low noise nanopore-based ionic current recording under laser illumination

NASA Astrophysics Data System (ADS)

Roelen, Zachary; Bustamante, José A.; Carlsen, Autumn; Baker-Murray, Aidan; Tabard-Cossa, Vincent

2018-01-01

We describe a nanopore-based optofluidic instrument capable of performing low-noise ionic current recordings of individual biomolecules under laser illumination. In such systems, simultaneous optical measurements generally introduce significant parasitic noise in the electrical signal, which can severely reduce the instrument sensitivity, critically hindering the monitoring of single-molecule events in the ionic current traces. Here, we present design rules and describe simple adjustments to the experimental setup to mitigate the different noise sources encountered when integrating optical components to an electrical nanopore system. In particular, we address the contributions to the electrical noise spectra from illuminating the nanopore during ionic current recording and mitigate those effects through control of the illumination source and the use of a PDMS layer on the SiNx membrane. We demonstrate the effectiveness of our noise minimization strategies by showing the detection of DNA translocation events during membrane illumination with a signal-to-noise ratio of ˜10 at 10 kHz bandwidth. The instrumental guidelines for noise minimization that we report are applicable to a wide range of nanopore-based optofluidic systems and offer the possibility of enhancing the quality of synchronous optical and electrical signals obtained during single-molecule nanopore-based analysis.

Brownian dynamics simulation of a polymer chain in a solid-state nanopore attached to a molecular stop

NASA Astrophysics Data System (ADS)

Wells, Craig; Hulings, Zachery; Melnikov, Dmitriy; Gracheva, Maria

We study a nanopore inside a silicon dioxide membrane submerged in a KCl solution with a negatively charged polymer chain of varying lengths whose movement is described using Brownian dynamics. The polymer is attached to a molecule with a radius larger than that of the nanopore's which acts as a molecular stop, allowing the chain to thread the nanopore but preventing it from translocating. We found that the polymer chain's variation of movement along the nanopore decreased when increasing applied biases and chain lengths for portions of the chain closest to the molecular stop. The chain displacement within the pore is also compared to a freely translocating polymer where preliminary results show the free polymer having a greater variation in the radial direction. Overall, our preliminary results indicate that the radial direction of the polymer chain is dominated by the confinement in the narrow nanopore with restrictions imposed by the molecular stop and bias playing a lesser role. Understanding the interaction behavior of the polymer chain-stop molecule may lead to methods that decrease movement variation, facilitating an improvement on characterizing and identification of molecules. NSF DMR and CBET Grant No. 1352218.

Poly(ethylene glycol)s in Semidilute Regime: Radius of Gyration in the Bulk and Partitioning into a Nanopore

DOE PAGES

Gurnev, Philip A.; Stanley, Christopher B.; Aksoyoglu, M. Alphan; ...

2017-03-09

In this work, using two approaches, small-angle neutron scattering (SANS) from bulk solutions and nanopore conductance-fluctuation analysis, we studied structural and dynamic features of poly(ethylene glycol) (PEG) water/salt solutions in the dilute and semidilute regimes. SANS measurements on PEG 3400 at the zero-average contrast yielded the single chain radius of gyration (R g) over 1–30 wt %. We observed a small but statistically reliable decrease in R g with increasing PEG concentration: at 30 wt % the chain contracts by a factor of 0.94. Analyzing conductance fluctuations of the α-hemolysin nanopore in the mixtures of PEG 200 with PEG 3400,more » we demonstrated that polymer partitioning into the nanopore is mostly due to PEG 200. Specifically, for a 1:1 wt/wt mixture the smaller polymer dominates to the extent that only about 1/25 of the nanopore volume is taken by the larger polymer. In conclusion, these findings advance our conceptual and quantitative understanding of nanopore polymer partitioning; they also support the main assumptions of the recent “polymers-pushing-polymers” model.« less

Nanopore extended field-effect transistor for selective single-molecule biosensing.

PubMed

Ren, Ren; Zhang, Yanjun; Nadappuram, Binoy Paulose; Akpinar, Bernice; Klenerman, David; Ivanov, Aleksandar P; Edel, Joshua B; Korchev, Yuri

2017-09-19

There has been a significant drive to deliver nanotechnological solutions to biosensing, yet there remains an unmet need in the development of biosensors that are affordable, integrated, fast, capable of multiplexed detection, and offer high selectivity for trace analyte detection in biological fluids. Herein, some of these challenges are addressed by designing a new class of nanoscale sensors dubbed nanopore extended field-effect transistor (nexFET) that combine the advantages of nanopore single-molecule sensing, field-effect transistors, and recognition chemistry. We report on a polypyrrole functionalized nexFET, with controllable gate voltage that can be used to switch on/off, and slow down single-molecule DNA transport through a nanopore. This strategy enables higher molecular throughput, enhanced signal-to-noise, and even heightened selectivity via functionalization with an embedded receptor. This is shown for selective sensing of an anti-insulin antibody in the presence of its IgG isotype.Efficient detection of single molecules is vital to many biosensing technologies, which require analytical platforms with high selectivity and sensitivity. Ren et al. combine a nanopore sensor and a field-effect transistor, whereby gate voltage mediates DNA and protein transport through the nanopore.

Silicon deposition in nanopores using a liquid precursor.

PubMed

Masuda, Takashi; Tatsuda, Narihito; Yano, Kazuhisa; Shimoda, Tatsuya

2016-11-22

Techniques for depositing silicon into nanosized spaces are vital for the further scaling down of next-generation devices in the semiconductor industry. In this study, we filled silicon into 3.5-nm-diameter nanopores with an aspect ratio of 70 by exploiting thermodynamic behaviour based on the van der Waals energy of vaporized cyclopentasilane (CPS). We originally synthesized CPS as a liquid precursor for semiconducting silicon. Here we used CPS as a gas source in thermal chemical vapour deposition under atmospheric pressure because vaporized CPS can fill nanopores spontaneously. Our estimation of the free energy of CPS based on Lifshitz van der Waals theory clarified the filling mechanism, where CPS vapour in the nanopores readily undergoes capillary condensation because of its large molar volume compared to those of other vapours such as water, toluene, silane, and disilane. Consequently, a liquid-specific feature was observed during the deposition process; specifically, condensed CPS penetrated into the nanopores spontaneously via capillary force. The CPS that filled the nanopores was then transformed into solid silicon by thermal decomposition at 400 °C. The developed method is expected to be used as a nanoscale silicon filling technology, which is critical for the fabrication of future quantum scale silicon devices.

Silicon deposition in nanopores using a liquid precursor

NASA Astrophysics Data System (ADS)

Masuda, Takashi; Tatsuda, Narihito; Yano, Kazuhisa; Shimoda, Tatsuya

2016-11-01

Techniques for depositing silicon into nanosized spaces are vital for the further scaling down of next-generation devices in the semiconductor industry. In this study, we filled silicon into 3.5-nm-diameter nanopores with an aspect ratio of 70 by exploiting thermodynamic behaviour based on the van der Waals energy of vaporized cyclopentasilane (CPS). We originally synthesized CPS as a liquid precursor for semiconducting silicon. Here we used CPS as a gas source in thermal chemical vapour deposition under atmospheric pressure because vaporized CPS can fill nanopores spontaneously. Our estimation of the free energy of CPS based on Lifshitz van der Waals theory clarified the filling mechanism, where CPS vapour in the nanopores readily undergoes capillary condensation because of its large molar volume compared to those of other vapours such as water, toluene, silane, and disilane. Consequently, a liquid-specific feature was observed during the deposition process; specifically, condensed CPS penetrated into the nanopores spontaneously via capillary force. The CPS that filled the nanopores was then transformed into solid silicon by thermal decomposition at 400 °C. The developed method is expected to be used as a nanoscale silicon filling technology, which is critical for the fabrication of future quantum scale silicon devices.

Nanostructural Engineering of Nanoporous Anodic Alumina for Biosensing Applications

PubMed Central

Ferré-Borrull, Josep; Pallarès, Josep; Macías, Gerard; Marsal, Lluis F.

2014-01-01

Modifying the diameter of the pores in nanoporous anodic alumina opens new possibilities in the application of this material. In this work, we review the different nanoengineering methods by classifying them into two kinds: in situ and ex situ. Ex situ methods imply the interruption of the anodization process and the addition of intermediate steps, while in situ methods aim at realizing the in-depth pore modulation by continuous changes in the anodization conditions. Ex situ methods permit a greater versatility in the pore geometry, while in situ methods are simpler and adequate for repeated cycles. As an example of ex situ methods, we analyze the effect of changing drastically one of the anodization parameters (anodization voltage, electrolyte composition or concentration). We also introduce in situ methods to obtain distributed Bragg reflectors or rugate filters in nanoporous anodic alumina with cyclic anodization voltage or current. This nanopore engineering permits us to propose new applications in the field of biosensing: using the unique reflectance or photoluminescence properties of the material to obtain photonic barcodes, applying a gold-coated double-layer nanoporous alumina to design a self-referencing protein sensor or giving a proof-of-concept of the refractive index sensing capabilities of nanoporous rugate filters. PMID:28788127

Multifunctional nanopipette for simultaneous ionic current and potential detection of nanoparticles

NASA Astrophysics Data System (ADS)

Panday, Namuna; He, Jin

Nanopipette has been demonstrated as a nanopore type biosensor for DNA, protein, nanoparticle and virus analysis. In the last two decades, nanopore based technologies have made remarkable progress for single entity detection and analysis. Multifunctional nanopipette for multi-parameter detection is a new trend for nanopore based technique. We have developed a technique to fabricate multifunctional nanopipette which contains both nanopore and carbon nanoelectrode (CNE) at the nanopipette tip. It can be quickly, cheaply and reproducibly fabricated from theta pipettes. We have been able to use this multifunctional nanopieptte for simultaneous detection of ionic current and local electrical potential changes during translocation of charged gold nanoparticles (GNPs) which is used as a model experiment. The CNE functions as a local potential probe. We have demonstrated that it can detect the local potential change during translocation of a single GNP as well as collective potential change due to cluster of GNPs outside the nanopore entrance. From the potential change, we can also have insight of motion of GNPs before entering the nanopore. We have also tested insulating and biological NPs with various size and charge. Observed results have shown correlations between ionic current and potential change during translocation of these NPs. Florida International University.

Rapid self-assembly of block copolymers to photonic crystals

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R; Grubbs, Robert H; Weitekamp, Raymond; Miyake, Garret M; Atwater, Harry A; Piunova, Victoria; Daeffler, Christopher Scot; Hong, Sung Woo; Gu, Weiyin; Russell, Thomas P.

2016-07-05

The invention provides a class of copolymers having useful properties, including brush block copolymers, wedge-type block copolymers and hybrid wedge and polymer block copolymers. In an embodiment, for example, block copolymers of the invention incorporate chemically different blocks comprising polymer size chain groups and/or wedge groups that significantly inhibit chain entanglement, thereby enhancing molecular self-assembly processes for generating a range of supramolecular structures, such as periodic nanostructures and microstructures. The present invention also provides useful methods of making and using copolymers, including block copolymers.

Science of Nanofluidics and Energy Conversion

NASA Astrophysics Data System (ADS)

Xu, Baoxing

The emerging subject of nanofluidics, where solids and fluids interact closely at the nanoscale, has exhibited radically different from their macroscopic counterparts (and sometimes counterintuitive), and yet relatively less explored. On the other hand, the resulting unique properties may contribute to a number of innovative functions with fascinating applications. Among various exciting potential applications, an important and ever expanding one is to provide alternative solutions to energy conversion with high efficiency, including energy absorption, actuation and harvesting. In this dissertation, we first report a novel protection mechanism of energy capture through which an intensive impact or blast energy can be effectively mitigated based on a nonwetting liquid-nanoporous material system. The captured energy is stored in nanopores in the form of potential energy of intercalated water molecules for a while, and not necessarily converted to other forms of energy (e.g. heat). At unloading stage, the captured energy will be released gradually due to the hydrophobic inner surfaces of nanopores through the diffusion of water molecules out of nanopores, thus making this system reusable. Several key controlling factors including impacting velocity, nanopore size, nanopore structure, and liquid phase have been investigated on the capacity of energy capture. The molecular mechanism is elucidated through the study of water molecular distributions inside nanpores. These molecular dynamic (MD) findings are quantitatively verified by a parallel blast experiment on a zeolite/water system. During the transport of confined liquid molecules, the friction resistance exerted by solid atoms of nanopores to liquid molecules will dissipate part of energy, and is highly dependent of temperature of liquid molecules and wall morphology of nanopores. Using MD simulations, the effects of temperature and wall roughness on the transport resistance of water molecules inside nanopores are investigated in Chapter 3. The effective shear stress and nominal viscosity that dominate the nanofluidic transport resistance are extracted and coupled with the nanopore size, transport rate, and liquid property. The molecular-level mechanisms are revealed through the study of the density profile and hydrogen bonding of confined liquid molecules. A parallel experiment on a nanoporous carbon-liquid system is carried out and qualitatively verifies MD findings. Motived by the well-known thermo- and electro-capillary effect, Chapter 4 and Chapter 5 present a conceptual design of thermal and electric actuation system by adjusting the relative hydrophobicity of a liquid-nanoporous system through a thermal and electric field, respectively. The thermally and electrically dependent infiltration behaviors of liquids into nanopores are analyzed by using MD simulations. The fundamental molecular characteristics, including the density profile, contact angle, and surface tension of the confined liquid molecules, are examined to reveal underlying mechanisms. The energy density, power density, and efficiency of both thermal and electric actuation systems are explored and their variations with pore size, solid phase, and liquid phase are evaluated. Thermally and electrically controlled infiltration experiments on a zeolite-water /electrolyte solution system are performed accordingly to qualitatively validate these findings. These energy actuation systems can also become high density thermal or electric storage devices with proper designs. Energy harvesting by the flow of a hydrochloric acid-water solution through a nanopore is explored using atomistic simulations in the last chapter. Through ion configurations near the pore wall, an averaged ion drifting velocity is determined, and the induced voltage along the axial direction is obtained as a function of key material parameters, including the applied flow rate, environmental temperature, solution concentration and nanopore size. The molecular mechanism of ion hopping and motion is revealed. This study shed light on harvesting wasted thermal and mechanical energy from ambient environmental sources such as wasted heat in power plants. Nanofluidics is a novel and thriving research area, whose couplings with other disciplines such as material, mechanical, physical, chemical, electrical engineering are open.

Nanoporous SiC: a candidate semi-permeable material for biomedical applications.

PubMed

Rosenbloom, A J; Sipe, D M; Shishkin, Y; Ke, Y; Devaty, R P; Choyke, W J

2004-12-01

We have fabricated free-standing SiC nanoporous membranes in both p -type and n -type material. We showed that these membranes will permit the diffusion of proteins up to 29000 Daltons, while excluding larger proteins. By using radioactively labeled albumin, we also show that porous SiC has very low protein adsorption, comparable to the best commercially available polymer nanoporous membrane.

Initiation of explosive conversions in energy-saturated nanoporous silicon-based compounds with fast semiconductor switches and energy-releasing elements

NASA Astrophysics Data System (ADS)

Savenkov, G. G.; Kardo-Sysoev, A. F.; Zegrya, A. G.; Os'kin, I. A.; Bragin, V. A.; Zegrya, G. G.

2017-10-01

The first findings concerning the initiation of explosive conversions in energy-saturated nanoporous silicon-based compounds via the electrical explosion of a semiconductor bridge are presented. The obtained results indicate that the energy parameters of an explosive conversion depend on the mass of a combustible agent—namely, nanoporous silicon—and the silicon-doping type.

Nucleobase recognition at alkaline pH and apparent pKa of single DNA bases immobilised within a biological nanopore.

PubMed

Franceschini, Lorenzo; Mikhailova, Ellina; Bayley, Hagan; Maglia, Giovanni

2012-02-01

The four DNA bases are recognized in immobilized DNA strands at high alkaline pH by nanopore current recordings. Ionic currents through the biological nanopores are also employed to measure the apparent pK(a) values of single nucleobases within the immobilised DNA strands. This journal is © The Royal Society of Chemistry 2012

Immobilization of folic acid on Eu3+-doped nanoporous silica spheres.

PubMed

Tagaya, Motohiro; Ikoma, Toshiyuki; Yoshioka, Tomohiko; Xu, Zhefeng; Tanaka, Junzo

2011-08-07

Folic acid (FA) was immobilized on Eu(3+)-doped nanoporous silica spheres (Eu:NPSs) through mediation of the 3-aminopropyltriethoxysilane adlayer. The ordered nanopores of Eu:NPS were preserved by the immobilization. The FA-immobilized Eu:NPSs showed the characteristic photoluminescence peak due to interactions between the FA molecules and Eu(3+) ions, and highly dispersed stability in phosphate buffered saline.

Probing the size of proteins with glass nanopores

NASA Astrophysics Data System (ADS)

Steinbock, L. J.; Krishnan, S.; Bulushev, R. D.; Borgeaud, S.; Blokesch, M.; Feletti, L.; Radenovic, A.

2014-11-01

Single molecule studies using nanopores have gained attention due to the ability to sense single molecules in aqueous solution without the need to label them. In this study, short DNA molecules and proteins were detected with glass nanopores, whose sensitivity was enhanced by electron reshaping which decreased the nanopore diameter and created geometries with a reduced sensing length. Further, proteins having molecular weights (MW) ranging from 12 kDa to 480 kDa were detected, which showed that their corresponding current peak amplitude changes according to their MW. In the case of the 12 kDa ComEA protein, its DNA-binding properties to an 800 bp long DNA molecule was investigated. Moreover, the influence of the pH on the charge of the protein was demonstrated by showing a change in the translocation direction. This work emphasizes the wide spectrum of detectable molecules using nanopores from glass nanocapillaries, which stand out because of their inexpensive, lithography-free, and rapid manufacturing process.Single molecule studies using nanopores have gained attention due to the ability to sense single molecules in aqueous solution without the need to label them. In this study, short DNA molecules and proteins were detected with glass nanopores, whose sensitivity was enhanced by electron reshaping which decreased the nanopore diameter and created geometries with a reduced sensing length. Further, proteins having molecular weights (MW) ranging from 12 kDa to 480 kDa were detected, which showed that their corresponding current peak amplitude changes according to their MW. In the case of the 12 kDa ComEA protein, its DNA-binding properties to an 800 bp long DNA molecule was investigated. Moreover, the influence of the pH on the charge of the protein was demonstrated by showing a change in the translocation direction. This work emphasizes the wide spectrum of detectable molecules using nanopores from glass nanocapillaries, which stand out because of their inexpensive, lithography-free, and rapid manufacturing process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05001k

A Facile Method to Fabricate Double Gyroid as A Polymer Template for Nanohybrids

NASA Astrophysics Data System (ADS)

Wang, Hsiao-Fang; Ho, Rong-Ming

2015-03-01

Here, we suggest a facile method to acquire double gyroid (DG) phase from the self-assembly of chiral block copolymers (BCPs*), polystyrene- b-poly(L-lactide) (PS-PLLA). A wide region for the formation of DG can be found in the phase diagram of the BCPs*, suggesting that helical phase (H*) from the self-assembly of BCPs* can serve as a stepping stone for the formation of the DG due to an easy path for order-order transition from two-dimensional to three-dimensional (network) structure. Moreover, the order-order transition from metastable H* to stable DG can be expedited by blending the PS-PLLA with compatible entity. Moreover, PS-PLLA blends are prepared by using styrene oligomer (S) to fine-tune the morphologies of the blends at which the molecular weight ratio of the S and compatible PS block (r) is less than 0.1. Owing to the use of the low-molecular-weight oligomer, the increase of BCP chain mobility in the blends significantly reduces the transformation time for the order-order transition from H* to DG. Consequently, nanoporous gyroid SiO2 can be fabricated using hydrolyzed PS-PLLA blends as a template for sol-gel reaction followed by removal of the PS matrix.

Building membrane nanopores

NASA Astrophysics Data System (ADS)

Howorka, Stefan

2017-07-01

Membrane nanopores--hollow nanoscale barrels that puncture biological or synthetic membranes--have become powerful tools in chemical- and biosensing, and have achieved notable success in portable DNA sequencing. The pores can be self-assembled from a variety of materials, including proteins, peptides, synthetic organic compounds and, more recently, DNA. But which building material is best for which application, and what is the relationship between pore structure and function? In this Review, I critically compare the characteristics of the different building materials, and explore the influence of the building material on pore structure, dynamics and function. I also discuss the future challenges of developing nanopore technology, and consider what the next-generation of nanopore structures could be and where further practical applications might emerge.

Nanoporous metallic surface: Facile fabrication and enhancement of boiling heat transfer

NASA Astrophysics Data System (ADS)

Tang, Yong; Tang, Biao; Qing, Jianbo; Li, Qing; Lu, Longsheng

2012-09-01

The paper reports a flexible and low-cost approach, hot-dip galvanizing and dealloying, for the fabrication of enhanced nanoporous metallic surfaces. A Cu-Zn alloy layer mainly composed of γ-Cu5Zn8 and β'-CuZn was formed during the hot-dipping process. The multiple oxidation peaks recorded in the anodic liner sweep voltammetry measurements indicate different dezincification preferences of the alloy phases. A nanoporous copper surface with approximately 50-200 nm in pore size was obtained after a free corrosion process. The nanoporous structure improves the surface wettability and shows dramatic reduction of wall superheat compared to that of the plain surface in the pool-boiling experiments.

Enhancing the platinum atomic layer deposition infiltration depth inside anodic alumina nanoporous membrane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaish, Amit, E-mail: anv@udel.edu; Krueger, Susan; Dimitriou, Michael

Nanoporous platinum membranes can be straightforwardly fabricated by forming a Pt coating inside the nanopores of anodic alumina membranes (AAO) using atomic layer deposition (ALD). However, the high-aspect-ratio of AAO makes Pt ALD very challenging. By tuning the process deposition temperature and precursor exposure time, enhanced infiltration depth along with conformal coating was achieved for Pt ALD inside the AAO templates. Cross-sectional scanning electron microscopy/energy dispersive x-ray spectroscopy and small angle neutron scattering were employed to analyze the Pt coverage and thickness inside the AAO nanopores. Additionally, one application of platinum-coated membrane was demonstrated by creating a high-density protein-functionalized interface.

Nanopore with Transverse Nanoelectrodes for Electrical Characterization and Sequencing of DNA

PubMed Central

Gierhart, Brian C.; Howitt, David G.; Chen, Shiahn J.; Zhu, Zhineng; Kotecki, David E.; Smith, Rosemary L.; Collins, Scott D.

2009-01-01

A DNA sequencing device which integrates transverse conducting electrodes for the measurement of electrode currents during DNA translocation through a nanopore has been nanofabricated and characterized. A focused electron beam (FEB) milling technique, capable of creating features on the order of 1 nm in diameter, was used to create the nanopore. The device was characterized electrically using gold nanoparticles as an artificial analyte with both DC and AC measurement methods. Single nanoparticle/electrode interaction events were recorded. A low-noise, high-speed transimpedance current amplifier for the detection of nano to picoampere currents at microsecond time scales was designed, fabricated and tested for future integration with the nanopore device. PMID:19584949

Nanopore with Transverse Nanoelectrodes for Electrical Characterization and Sequencing of DNA.

PubMed

Gierhart, Brian C; Howitt, David G; Chen, Shiahn J; Zhu, Zhineng; Kotecki, David E; Smith, Rosemary L; Collins, Scott D

2008-06-16

A DNA sequencing device which integrates transverse conducting electrodes for the measurement of electrode currents during DNA translocation through a nanopore has been nanofabricated and characterized. A focused electron beam (FEB) milling technique, capable of creating features on the order of 1 nm in diameter, was used to create the nanopore. The device was characterized electrically using gold nanoparticles as an artificial analyte with both DC and AC measurement methods. Single nanoparticle/electrode interaction events were recorded. A low-noise, high-speed transimpedance current amplifier for the detection of nano to picoampere currents at microsecond time scales was designed, fabricated and tested for future integration with the nanopore device.

Synthesis of highly nanoporous YBO3 architecture via a co-precipitation approach and tunable luminescent properties.

PubMed

Liu, Lili; Zhang, Xianwen; Chaudhuri, Jharna

2015-01-01

We present a simple co-precipitation method to prepare highly nanoporous YBO(3) architecture using NaBO(3) ·  4H(2)O as a boric source and 600°C as the annealing temperature. The reaction was carried out under an aqueous condition without any organic solvent, surfactant, or catalysts. The prepared samples were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The photoluminescence of doped-nanoporous YBO(3):Eu(3+) was further investigated. It is expected that highly nanoporous YBO(3) architecture can be an ideal candidate for applications in catalysis, adsorption, and optoelectronic devices. © Wiley Periodicals, Inc.

Influence of nanoporosity on biological response of sol-gel-derived 70S30C bioactive glass monoliths

NASA Astrophysics Data System (ADS)

Thamma, Ukrit

In the field of bioactive glasses for hard tissue regeneration, the bioactivity of a material is measured by its ability to induce the formation of hydroxyapatite (HA), Ca10(PO4)6(OH)2, under physiological conditions. Due to its close chemical crystallographic resemblance to natural bones, the newly formed HA layer has been shown to be critical for the biological interaction and bonding between the surfaces of bioactive glasses and osteoblast (bone) cells. Since the formation mechanism of HA is dependent on the dissolution behavior of the bioactive glass substrate, the characteristics of HA layer are dominated by the glass composition and structure. By introducing nanoporosity into glass structure, the dissolution rate and HA growth rate on nanoporous sol-gel-derived glasses are drastically enhanced compared to that of non-porous melt-quench glasses with the same composition. While enhanced HA growth on nanoporous glass, compared to non-porous glass, was hypothesized to be associated with greater specific surface area (SSA), other studies argued that growth rate of HA layer on nanoporous glass is dominated by nanopore size distribution, and minimally affected by the bulk SSA of the underlying glass. In order to decouple the influence of nanopore size and SSA on HA formation, we have successfully fabricated homogeneous 70S30C bioactive glass monoliths with different nanopore sizes, yet similar SSA via sol-gel process. After 3-day PBS incubation of 70S30C nanoporous glass monoliths, the presence of hydroxyapatite and Type-B carbonated hydroxyapatite (HA/B-CHA) was confirmed by XPS and FTIR. Here, we report the influence of nanopore size on HA/CHA formation pathway, growth rate, and its microstructure. Due to pore-size limited diffusion of PO43-, two HA/CHA formation pathways were observed: HA/CHA surface deposition and/or HA/CHA incorporation into nanopores. HA/CHA growth rate on the surface of a nanoporous glass monolith is dominated by the pore-size limited transport of Ca2+ ions dissolved from nanoporous glass substrates. Furthermore, with rising overall growth rate controlled by nanopore size, HA/CHA microstructures evolved from needle-like, plate-like, and flower-like, respectively. Furthermore, the levels of initial cell attachment and protein adsorption on HA/CHA microstructures formed on different nanopore sizes were investigated. The initial cell attachment was quantified by measuring the density and average size of attached MC3T3-E1 cells after 2-hour seeding period. The amounts and conformation of adsorbed proteins after 2-hour incubation with HA/CHA were characterized by Western blot and FTIR, respectively. It was shown that the amounts of protein adsorption on various HA/CHA microstructures do not correlate with the initial MC3T3-E1 attachment, while the beta-sheet/alpha-helix ratios in Amide I of bovine albumin serum (BSA) adsorbed on HA/CHA microstructures do correlate to the level of initial cell attachment. This result suggests that the beta-sheet structure in BSA interacts with and activates the RGD sequence of adhesion proteins, such as fibronectin, upon adsorption, thus significantly enhancing the initial attachment of MC3T3-E1 cells. These findings provide new insights that can lead to a more detailed fundamental understanding of protein-surface and protein-protein interactions, which are crucial for the further development of bioactive material.

Molecular simulation of simple fluids and polymers in nanoconfinement

NASA Astrophysics Data System (ADS)

Rasmussen, Christopher John

Prediction of phase behavior and transport properties of simple fluids and polymers confined to nanoscale pores is important to a wide range of chemical and biochemical engineering processes. A practical approach to investigate nanoscale systems is molecular simulation, specifically Monte Carlo (MC) methods. One of the most challenging problems is the need to calculate chemical potentials in simulated phases. Through the seminal work of Widom, practitioners have a powerful method for calculating chemical potentials. Yet, this method fails for dense and inhomogeneous systems, as well as for complex molecules such as polymers. In this dissertation, the gauge cell MC method, which had previously been successfully applied to confined simple fluids, was employed and extended to investigate nanoscale fluids in several key areas. Firstly, the process of cavitation (the formation and growth of bubbles) during desorption of fluids from nanopores was investigated. The dependence of cavitation pressure on pore size was determined with gauge cell MC calculations of the nucleation barriers correlated with experimental data. Additional computational studies elucidated the role of surface defects and pore connectivity in the formation of cavitation bubbles. Secondly, the gauge cell method was extended to polymers. The method was verified against the literature results and found significantly more efficient. It was used to examine adsorption of polymers in nanopores. These results were applied to model the dynamics of translocation, the act of a polymer threading through a small opening, which is implicated in drug packaging and delivery, and DNA sequencing. Translocation dynamics was studied as diffusion along the free energy landscape. Thirdly, we show how computer simulation of polymer adsorption could shed light on the specifics of polymer chromatography, which is a key tool for the analysis and purification of polymers. The quality of separation depends on the physico-chemical mechanisms of polymer/pore interaction. We considered liquid chromatography at critical conditions, and calculated the dependence of the partition coefficient on chain length. Finally, solvent-gradient chromatography was modeled using a statistical model of polymer adsorption. A model for predicting separation of complex polymers (with functional groups or copolymers) was developed for practical use in chromatographic separations.

PREFACE New developments in nanopore research—from fundamentals to applications New developments in nanopore research—from fundamentals to applications

NASA Astrophysics Data System (ADS)

Albrecht, Tim; Edel, Joshua B.; Winterhalter, Mathias

2010-11-01

Biological and solid-state nanopores are an exciting field of research, which has seen a rapid development over the last 10 to 20 years. Activities in this area range from theoretical and experimental work on the underlying fundamental (bio)physics to applications in single-molecule biosensing. And while the prospect of DNA sequencing continues to be a major driving force, other applications with potentially similar impact begin to emerge, for example the detection of small molecules, proteins, protein/protein and protein/DNA complexes, and RNA to name just a few. It has also become apparent that both classes of nanopore devices have intrinsic advantages and disadvantages; hybrid structures combining the better of the two worlds would be a logical consequence and are beginning to appear in the literature. Many other highly innovative ideas and concepts continue to emerge and the number of nanopore-related publications has increased drastically over recent years. We found that more than 100 research groups worldwide are active in this area; several commercial settings are in the process of translating fundamental research into real-life applications. We therefore felt that now is the right time to showcase these new developments in a special issue: to inspire researchers active in the field, to liberate inherent synergies, and not least, to demonstrate to the outside world the current state-of-the-art and future opportunities. The title 'New developments in nanopore research—from fundamentals to applications' in some way reflects these ambitions and, even though not everyone invited was able to contribute, we were able to assemble 34 high-quality research papers from all over the world. We would like to acknowledge and thank all the contributors for their submissions, which made this special issue possible in the first place. Moreover, we would like to thank the staff at IOP Publishing for helping us with the administrative aspects and for coordinating the refereeing process, and Ms Natalia Goehring for the beautiful cover artwork. Finally, to the readers, we hope you find this special issue a valuable source of information and insight into the field of nanopores. New developments in nanopore research—from fundamentals to applications contents Mathematical modeling and simulation of nanopore blocking by precipitation M-T Wolfram, M Burger and Z S Siwy Protein conducting nanopores Anke Harsman, Vivien Krüger, Philipp Bartsch, Alf Honigmann, Oliver Schmidt, Sanjana Rao, Christof Meisinger and Richard Wagner Electrically sensing protease activity with nanopores Mikiembo Kukwikila and Stefan Howorka Electrical characterization of DNA-functionalized solid state nanopores for bio-sensing V Mussi, P Fanzio, L Repetto, G Firpo, P Scaruffi, S Stigliani, M Menotta, M Magnani, G P Tonini and U Valbusa Automatable lipid bilayer formation and ion channel measurement using sessile droplets J L Poulos, S A Portonovo, H Bang and J J Schmidt Critical assessment of OmpF channel selectivity: merging information from different experimental protocols M L López, E García-Giménez, V M Aguilella and A Alcaraz Chemically modified solid state nanopores for high throughput nanoparticle separation Anmiv S Prabhu, Talukder Zaki N Jubery, Kevin J Freedman, Rafael Mulero, Prashanta Dutta and Min Jun Kim Changes in ion channel geometry resolved to sub-ångström precision via single molecule mass spectrometry Joseph W F Robertson, John J Kasianowicz and Joseph E Reiner Entropic transport of finite size particles W Riefler, G Schmid, P S Burada and P Hänggi Osmotic stress regulates the strength and kinetics of sugar binding to the maltoporin channel Philip A Gurnev, Daniel Harries, V Adrian Parsegian and Sergey M Bezrukov Detection of urea-induced internal denaturation of dsDNA using solid-state nanoporesn Alon Singer, Heiko Kuhn, Maxim Frank-Kamenetskii and Amit Meller Translocation events in a single-walled carbon nanotube Jin He, Hao Liu, Pei Pang, Di Cao and Stuart Lindsay Probing DNA with micro- and nanocapillaries and optical tweezers L J Steinbock, O Otto, D R Skarstam, S Jahn, C Chimerel, J L Gornall and U F Keyser Fabrication of nanopores with embedded annular electrodes and transverse carbon nanotube electrodes Zhijun Jiang, Mirna Mihovilovic, Jason Chan and Derek Stein Fabrication and electrical characterization of a pore-cavity-pore device D Pedone, M Langecker, A M Münzer, R Wei, R D Nagel and U Rant Use of tunable nanopore blockade rates to investigate colloidal dispersions G R Willmott, R Vogel, S S C Yu, L G Groenewegen, G S Roberts, D Kozak, W Anderson and M Trau Facilitated translocation of polypeptides through a single nanopore Robert Bikwemu, Aaron J Wolfe, Xiangjun Xing and Liviu Movileanu Mechanistic insight into gramicidin-based detection of protein-ligand interactions via sensitized photoinactivation Tatyana I Rokitskaya, Michael X Macrae, Steven Blake, Natalya S Egorova, Elena A Kotova, Jerry Yang and Yuri N Antonenko Sequence-dependent unfolding kinetics of DNA hairpins studied by nanopore force spectroscopy Stephan Renner, Andrey Bessonov, Ulrich Gerland and Friedrich C Simmel Hydration properties of mechanosensitive channel pores define the energetics of gating A Anishkin, B Akitake, K Kamaraju, C-S Chiang and S Sukharev Dynamic translocation of ligand-complexed DNA through solid-state nanopores with optical tweezers Andy Sischka, Andre Spiering, Maryam Khaksar, Miriam Laxa, Janine König, Karl-Josef Dietz and Dario Anselmetti Force fluctuations assist nanopore unzipping of DNA V Viasnoff, N Chiaruttini, J Muzard and U Bockelmann Control and reversal of the electrophoretic force on DNA in a charged nanopore Binquan Luan and Aleksei Aksimentiev The properties of the outer membrane localized Lipid A transporter LptD Raimund Haarmann, Mohamed Ibrahim, Mara Stevanovic, Rolf Bredemeier and Enrico Schleiff Structural and dynamical properties of the porins OmpF and OmpC: insights from molecular simulations Amit Kumar, Eric Hajjar, Paolo Ruggerone and Matteo Ceccarelli Dehydration and ionic conductance quantization in nanopores Michael Zwolak, James Wilson and Massimiliano Di Ventra Current oscillations generated by precipitate formation in the mixing zone between two solutions inside a nanopore Erik C Yusko, Yazan N Billeh and Michael Mayer Precise electrochemical fabrication of sub-20 nm solid-state nanopores for single-molecule biosensing Mariam Ayub, Aleksandar Ivanov, Jongin Hong, Phillip Kuhn, Emanuele Instuli, Joshua B Edel and Tim Albrecht The distribution of DNA translocation times in solid-state nanopores Jiali Li and David S Talaga Crowding effects in non-equilibrium transport through nano-channels A Zilman and G Bel Permeation through nanochannels: revealing fast kinetics Kozhinjampara R Mahendran, Pratik Raj Singh, Jürgen Arning, Stefan Stolte, Ulrich Kleinekathöfer and Mathias Winterhalter LILBID-mass spectrometry of the mitochondrial preprotein translocase TOM Frauke Mager, Lucie Sokolova, Julia Lintzel, Bernhard Brutschy and Stephan Nussberger Evidence that small proteins translocate through silicon nitride pores in a folded conformation Radu I Stefureac, Dhruti Trivedi, Andre Marziali and Jeremy S Lee Methods for controlling the pore properties of ultra-thin nanocrystalline silicon membranes D Z Fang, C C Striemer, T R Gaborski, J L McGrath and P M Fauchet

Template-Free Synthesis of Nanoporous Nickel and Alloys as Binder-Free Current Collectors of Li Ion Batteries.

PubMed

Lu, Liqiang; Andela, Paul; De Hosson, Jeff Th M; Pei, Yutao

2018-05-25

This paper reports a versatile template-free method based on the hydrogen reduction of metallic salts for the synthesis of nanoporous Ni and alloys. The approach involves thermal decomposition and reduction of metallic precursors followed with metal cluster nucleation and ligament growth. Topological disordered porous architectures of metals with a controllable distribution of pore size and ligament size ranging from tens of nanometers to micrometers are synthesized. The reduction processes are scrutinized through X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The formation mechanism of the nanoporous metal is qualitatively explained. The as-prepared nanoporous Ni was tested as binder-free current collectors for nickel oxalate anodes of lithium ion batteries. The nanoporous Ni electrodes deliver enhanced reversible capacities and cyclic performances compared with commercial Ni foam. It is confirmed that this synthesis method has versatility not only because it is suitable for different types of metallic salts precursors but also for various other metals and alloys.

Template-Free Synthesis of Nanoporous Nickel and Alloys as Binder-Free Current Collectors of Li Ion Batteries

PubMed Central

2018-01-01

This paper reports a versatile template-free method based on the hydrogen reduction of metallic salts for the synthesis of nanoporous Ni and alloys. The approach involves thermal decomposition and reduction of metallic precursors followed with metal cluster nucleation and ligament growth. Topological disordered porous architectures of metals with a controllable distribution of pore size and ligament size ranging from tens of nanometers to micrometers are synthesized. The reduction processes are scrutinized through X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The formation mechanism of the nanoporous metal is qualitatively explained. The as-prepared nanoporous Ni was tested as binder-free current collectors for nickel oxalate anodes of lithium ion batteries. The nanoporous Ni electrodes deliver enhanced reversible capacities and cyclic performances compared with commercial Ni foam. It is confirmed that this synthesis method has versatility not only because it is suitable for different types of metallic salts precursors but also for various other metals and alloys. PMID:29911687

Nanopore Kinetic Proofreading of DNA Sequences

NASA Astrophysics Data System (ADS)

Ling, Xinsheng Sean

The concept of DNA sequencing using the time dependence of the nanopore ionic current was proposed in 1996 by Kasianowicz, Brandin, Branton, and Deamer (KBBD). The KBBD concept has generated tremendous amount interests in recent decade. In this talk, I will review the current understanding of the DNA ``translocation'' dynamics and how it can be described by Schrodinger's 1915 paper on first-passage-time distribution function. Schrodinger's distribution function can be used to give a rigorous criterion for achieving nanopore DNA sequencing which turns out to be identical to that of gel electrophoresis used by Sanger in the first-generation Sanger method. A nanopore DNA sequencing technology also requires discrimination of bases with high accuracies. I will describe a solid-state nanopore sandwich structure that can function as a proofreading device capable of discriminating between correct and incorrect hybridization probes with an accuracy rivaling that of high-fidelity DNA polymerases. The latest results from Nanjing will be presented. This work is supported by China 1000-Talent Program at Southeast University, Nanjing, China.

Fabrication of complete titania nanoporous structures via electrochemical anodization of Ti

PubMed Central

2011-01-01

We present a novel method to fabricate complete and highly oriented anodic titanium oxide (ATO) nano-porous structures with uniform and parallel nanochannels. ATO nano-porous structures are fabricated by anodizing a Ti-foil in two different organic viscous electrolytes at room temperature using a two-step anodizing method. TiO2 nanotubes covered with a few nanometer thin nano-porous layer is produced when the first and the second anodization are carried out in the same electrolyte. However, a complete titania nano-porous (TNP) structures are obtained when the second anodization is conducted in a viscous electrolyte when compared to the first one. TNP structure was attributed to the suppression of F-rich layer dissolution between the cell boundaries in the viscous electrolyte. The structural morphologies were examined by field emission scanning electron microscope. The average pore diameter is approximately 70 nm, while the average inter-pore distance is approximately 130 nm. These TNP structures are useful to fabricate other nanostructure materials and nanodevices. PMID:21711844

A nanoporous alumina microelectrode array for functional cell-chip coupling.

PubMed

Wesche, Manuel; Hüske, Martin; Yakushenko, Alexey; Brüggemann, Dorothea; Mayer, Dirk; Offenhäusser, Andreas; Wolfrum, Bernhard

2012-12-14

The design of electrode interfaces has a strong impact on cell-based bioelectronic applications. We present a new type of microelectrode array chip featuring a nanoporous alumina interface. The chip is fabricated in a combination of top-down and bottom-up processes using state-of-the-art clean room technology and self-assembled generation of nanopores by aluminum anodization. The electrode characteristics are investigated in phosphate buffered saline as well as under cell culture conditions. We show that the modified microelectrodes exhibit decreased impedance compared to planar microelectrodes, which is caused by a nanostructuring effect of the underlying gold during anodization. The stability and biocompatibility of the device are demonstrated by measuring action potentials from cardiomyocyte-like cells growing on top of the chip. Cross sections of the cell-surface interface reveal that the cell membrane seals the nanoporous alumina layer without bending into the sub-50 nm apertures. The nanoporous microelectrode array device may be used as a platform for combining extracellular recording of cell activity with stimulating topographical cues.

Conformational Transitions and Stop-and-Go Nanopore Transport of Single Stranded DNA on Charged Graphene

PubMed Central

Shankla, Manish; Aksimentiev, Aleksei

2014-01-01

Control over interactions with biomolecules holds the key to applications of graphene in biotechnology. One such application is nanopore sequencing, where a DNA molecule is electrophoretically driven through a graphene nanopore. Here, we investigate how interactions of single-stranded DNA and a graphene membrane can be controlled by electrically biasing the membrane. The results of our molecular dynamics simulations suggest that electric charge on graphene can force a DNA homopolymer to adopt a range of strikingly different conformations. The conformational response is sensitive to even very subtle nucleotide modifications, such as DNA methylation. The speed of DNA motion through a graphene nanopore is strongly affected by the graphene charge: a positive charge accelerates the motion whereas a negative charge arrests it. As a possible application of the effect, we demonstrate stop-and-go transport of DNA controlled by the charge of graphene. Such on-demand transport of DNA is essential for realizing nanopore sequencing. PMID:25296960

Rapid ultrasensitive single particle surface-enhanced Raman spectroscopy using metallic nanopores.

PubMed

Cecchini, Michael P; Wiener, Aeneas; Turek, Vladimir A; Chon, Hyangh; Lee, Sangyeop; Ivanov, Aleksandar P; McComb, David W; Choo, Jaebum; Albrecht, Tim; Maier, Stefan A; Edel, Joshua B

2013-10-09

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 μs.

A Hybrid Semi-Digital Transimpedance Amplifier With Noise Cancellation Technique for Nanopore-Based DNA Sequencing.

PubMed

Hsu, Chung-Lun; Jiang, Haowei; Venkatesh, A G; Hall, Drew A

2015-10-01

Over the past two decades, nanopores have been a promising technology for next generation deoxyribonucleic acid (DNA) sequencing. Here, we present a hybrid semi-digital transimpedance amplifier (HSD-TIA) to sense the minute current signatures introduced by single-stranded DNA (ssDNA) translocating through a nanopore, while discharging the baseline current using a semi-digital feedback loop. The amplifier achieves fast settling by adaptively tuning a DC compensation current when a step input is detected. A noise cancellation technique reduces the total input-referred current noise caused by the parasitic input capacitance. Measurement results show the performance of the amplifier with 31.6 M Ω mid-band gain, 950 kHz bandwidth, and 8.5 fA/ √Hz input-referred current noise, a 2× noise reduction due to the noise cancellation technique. The settling response is demonstrated by observing the insertion of a protein nanopore in a lipid bilayer. Using the nanopore, the HSD-TIA was able to measure ssDNA translocation events.

Design and fabrication of a 3D-structured gold film with nanopores for local electric field enhancement in the pore

NASA Astrophysics Data System (ADS)

Grant-Jacob, James A.; Zin Oo, Swe; Carpignano, Francesca; Boden, Stuart A.; Brocklesby, William S.; Charlton, Martin D. B.; Melvin, Tracy

2016-02-01

Three-dimensionally structured gold membrane films with nanopores of defined, periodic geometries are designed and fabricated to provide the spatially localised enhancement of electric fields by manipulation of the plasmons inside nanopores. Square nanopores of different size and orientation relative to the pyramid are considered for films in aqueous and air environments, which allow for control of the position of electric fields within the structure. Designs suitable for use with 780 nm light were created. Here, periodic pyramidal cavities produced by potassium hydroxide etching to the {111} planes of (100) silicon substrates are used as templates for creating a periodic, pyramidal structured, free-standing thin gold film. Consistent with the findings from the theoretical studies, a nano-sized hole of 50 nm square was milled through the gold film at a specific location in the cavity to provide electric field control which can subsequently used for enhancement of fluorescence or Raman scattering of molecules in the nanopore.

Design and fabrication of a 3D-structured gold film with nanopores for local electric field enhancement in the pore.

PubMed

Grant-Jacob, James A; Oo, Swe Zin; Carpignano, Francesca; Boden, Stuart A; Brocklesby, William S; Charlton, Martin D B; Melvin, Tracy

2016-02-12

Three-dimensionally structured gold membrane films with nanopores of defined, periodic geometries are designed and fabricated to provide the spatially localised enhancement of electric fields by manipulation of the plasmons inside nanopores. Square nanopores of different size and orientation relative to the pyramid are considered for films in aqueous and air environments, which allow for control of the position of electric fields within the structure. Designs suitable for use with 780 nm light were created. Here, periodic pyramidal cavities produced by potassium hydroxide etching to the {111} planes of (100) silicon substrates are used as templates for creating a periodic, pyramidal structured, free-standing thin gold film. Consistent with the findings from the theoretical studies, a nano-sized hole of 50 nm square was milled through the gold film at a specific location in the cavity to provide electric field control which can subsequently used for enhancement of fluorescence or Raman scattering of molecules in the nanopore.

Nanopore sensing at ultra-low concentrations using single-molecule dielectrophoretic trapping

PubMed Central

Freedman, Kevin J.; Otto, Lauren M.; Ivanov, Aleksandar P.; Barik, Avijit; Oh, Sang-Hyun; Edel, Joshua B.

2016-01-01

Single-molecule techniques are being developed with the exciting prospect of revolutionizing the healthcare industry by generating vast amounts of genetic and proteomic data. One exceptionally promising route is in the use of nanopore sensors. However, a well-known complexity is that detection and capture is predominantly diffusion limited. This problem is compounded when taking into account the capture volume of a nanopore, typically 108–1010 times smaller than the sample volume. To rectify this disproportionate ratio, we demonstrate a simple, yet powerful, method based on coupling single-molecule dielectrophoretic trapping to nanopore sensing. We show that DNA can be captured from a controllable, but typically much larger, volume and concentrated at the tip of a metallic nanopore. This enables the detection of single molecules at concentrations as low as 5 fM, which is approximately a 103 reduction in the limit of detection compared with existing methods, while still maintaining efficient throughput. PMID:26732171

Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors

DOE PAGES

Jackson, Grayson L.; Perroni, Dominic V.; Mahanthappa, Mahesh K.

2017-10-03

Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. Here, we report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80°C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimentalmore » comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.« less

Nanoporous hard data: optical encoding of information within nanoporous anodic alumina photonic crystals.

PubMed

Santos, Abel; Law, Cheryl Suwen; Pereira, Taj; Losic, Dusan

2016-04-21

Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for developing advanced nanophotonic tools for a wide range of applications, including sensing, photonic tagging, self-reporting drug releasing systems and secure encoding of information.

Gold/silver coated nanoporous ceramic membranes: a new substrate for SERS studies

NASA Astrophysics Data System (ADS)

Kassu, A.; Robinson, P.; Sharma, A.; Ruffin, P. B.; Brantley, C.; Edwards, E.

2010-08-01

Surface Enhanced Raman Scattering (SERS) is a recently discovered powerful technique which has demonstrated sensitivity and selectivity for detecting single molecules of certain chemical species. This is due to an enhancement of Raman scattered light by factors as large as 1015. Gold and Silver-coated substrates fabricated by electron-beam lithography on Silicon are widely used in SERS technique. In this paper, we report the use of nanoporous ceramic membranes for SERS studies. Nanoporous membranes are widely used as a separation membrane in medical devices, fuel cells and other studies. Three different pore diameter sizes of commercially available nanoporous ceramic membranes: 35 nm, 55nm and 80nm are used in the study. To make the membranes SERS active, they are coated with gold/silver using sputtering techniques. We have seen that the membranes coated with gold layer remain unaffected even when immersed in water for several days. The results show that gold coated nanoporous membranes have sensitivity comparable to substrates fabricated by electron-beam lithography on Silicon substrates.

Conformational transitions and stop-and-go nanopore transport of single-stranded DNA on charged graphene

NASA Astrophysics Data System (ADS)

Shankla, Manish; Aksimentiev, Aleksei

2014-10-01

Control over interactions with biomolecules holds the key to applications of graphene in biotechnology. One such application is nanopore sequencing, where a DNA molecule is electrophoretically driven through a graphene nanopore. Here we investigate how interactions of single-stranded DNA and a graphene membrane can be controlled by electrically biasing the membrane. The results of our molecular dynamics simulations suggest that electric charge on graphene can force a DNA homopolymer to adopt a range of strikingly different conformations. The conformational response is sensitive to even very subtle nucleotide modifications, such as DNA methylation. The speed of DNA motion through a graphene nanopore is strongly affected by the graphene charge: a positive charge accelerates the motion, whereas a negative charge arrests it. As a possible application of the effect, we demonstrate stop-and-go transport of DNA controlled by the charge of graphene. Such on-demand transport of DNA is essential for realizing nanopore sequencing.

Nanoporous PbSe-SiO2 Thermoelectric Composites.

PubMed

Wu, Chao-Feng; Wei, Tian-Ran; Sun, Fu-Hua; Li, Jing-Feng

2017-11-01

Nanoporous architecture has long been predicted theoretically for its proficiency in suppressing thermal conduction, but less concerned as a practical approach for better thermoelectric materials hitherto probably due to its technical challenges. This article demonstrates a study on nanoporous PbSe-SiO 2 composites fabricated by a facile method of mechanical alloying assisted by subsequent wet-milling and then spark plasma sintering. Owing to the formation of random nanopores and additional interface scattering, the lattice thermal conductivity is limited to a value as low as 0.56 W m -1 K -1 at above 600 K, almost the same low level achieved by introducing nanoscale precipitates. Besides, the room-temperature electrical transport is found to be dominated by the grain-boundary potential barrier scattering, whose effect fades away with increasing temperatures. Consequently, a maximum ZT of 1.15 at 823 K is achieved in the PbSe + 0.7 vol% SiO 2 composition with >20% increase in average ZT , indicating the great potential of nanoporous structuring toward high thermoelectric conversion efficiency.

Nanoporous Polymers Based on Liquid Crystals

PubMed Central

Mulder, Dirk Jan; Sijbesma, Rint; Schenning, Albert

2018-01-01

In the present review, we discuss recent advances in the field of nanoporous networks based on polymerisable liquid crystals. The field has matured in the last decade, yielding polymers having 1D, 2D, and 3D channels with pore sizes on the nanometer scale. Next to the current progress, some of the future challenges are presented, with the integration of nanoporous membranes in functional devices considered as the biggest challenge. PMID:29324669

Self-grown oxy-hydroxide@ nanoporous metal electrode for high-performance supercapacitors.

PubMed

Kang, JianLi; Hirata, Akihiko; Qiu, H-J; Chen, LuYang; Ge, XingBo; Fujita, Takeshi; Chen, MingWei

2014-01-15

A binder-free self-grown oxy-hydroxide@nanoporous Ni-Mn hybrid electrode with high capacitance and cyclic stability is fabricated by electrochemical polarization of a dealloyed nanoporous Ni-Mn alloy. Combined with the low material costs, high electrochemical stability, and environmentally friendly nature, this novel electrode holds great promise for applications in high-capacity commercial supercapacitors. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of nanoporous metal foam from high nitrogen transition metal complexes

DOEpatents

Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

2006-11-28

Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

Carbon nanotube-based coatings to induce flow enhancement in hydrophilic nanopores

NASA Astrophysics Data System (ADS)

Wagemann, Enrique; Walther, J. H.; Zambrano, Harvey A.

2016-11-01

With the emergence of the field of nanofluidics, the transport of water in hydrophilic nanopores has attracted intensive research due to its many promising applications. Experiments and simulations have found that flow resistance in hydrophilic nanochannels is much higher than those in macrochannels. Indeed, this might be attributed to significant fluid adsorption on the channel walls and to the effect of the increased surface to volume ratio inherent to the nanoconfinement. Therefore, it is desirable to explore strategies for drag reduction in nanopores. Recently, studies have found that carbon nanotubes (CNTs) feature ultrafast water flow rates which result in flow enhancements of 1 to 5 orders of magnitude compared to Hagen-Poiseuille predictions. In the present study, CNT-based coatings are considered to induce water flow enhancement in silica nanopores with different radius. We conduct atomistic simulations of pressurized water flow inside tubular silica nanopores with and without inner coaxial carbon nanotubes. In particular, we compute water density and velocity profiles, flow enhancement and slip lengths to understand the drag reduction capabilities of single- and multi-walled carbon nanotubes implemented as coating material in silica nanopores. We wish to thank partial funding from CRHIAM and FONDECYT project 11130559, computational support from DTU and NLHPC (Chile).

Size effects of pore density and solute size on water osmosis through nanoporous membrane.

PubMed

Zhao, Kuiwen; Wu, Huiying

2012-11-15

Understanding the behavior of osmotic transport across nanoporous membranes at molecular level is critical to their design and applications, and it is also beneficial to the comprehension of the mechanism of biological transmembrane transport processes. Pore density is an important parameter for nanoporous membranes. To better understand the influence of pore density on osmotic transport, we have performed systematic molecular dynamics simulations on water osmosis across nanoporous membranes with different pore densities (i.e., number of pores per unit area of membrane). The simulation results reveal that significant size effects occur when the pore density is so high that the center-to-center distance between neighboring nanopores is comparable to the solute size. The size effects are independent of the pore diameter and solute concentration. A simple quantitative correlation between pore density, solute size, and osmotic flux has been established. The results are excellently consistent with the theoretical predictions. It is also shown that solute hydration plays an important role in real osmotic processes. Solute hydration strengthens the size effects of pore density on osmotic processes due to the enlarged effective solute size induced by hydration. The influence of pore density, solute size, and solute hydration on water osmosis through nanoporous membranes can be introduced to eliminate the deviations of real osmotic processes from ideal behavior.

Self-assembling synthesis of free-standing nanoporous graphene-transition-metal oxide flexible electrodes for high-performance lithium-ion batteries and supercapacitors.

PubMed

Huang, Xiaodan; Sun, Bing; Chen, Shuangqiang; Wang, Guoxiu

2014-01-01

The synthesis of nanoporous graphene by a convenient carbon nanofiber assisted self-assembly approach is reported. Porous structures with large pore volumes, high surface areas, and well-controlled pore sizes were achieved by employing spherical silica as hard templates with different diameters. Through a general wet-immersion method, transition-metal oxide (Fe3O4, Co3O4, NiO) nanocrystals can be easily loaded into nanoporous graphene papers to form three-dimensional flexible nanoarchitectures. When directly applied as electrodes in lithium-ion batteries and supercapacitors, the materials exhibited superior electrochemical performances, including an ultra-high specific capacity, an extended long cycle life, and a high rate capability. In particular, nanoporous Fe3O4-graphene composites can deliver a reversible specific capacity of 1427.5 mAh g(-1) at a high current density of 1000 mA g(-1) as anode materials in lithium-ion batteries. Furthermore, nanoporous Co3O4-graphene composites achieved a high supercapacitance of 424.2 F g(-1) . This work demonstrated that the as-developed freestanding nanoporous graphene papers could have significant potential for energy storage and conversion applications. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

15N and 31P solid-state NMR study of transmembrane domain alignment of M2 protein of influenza A virus in hydrated cylindrical lipid bilayers confined to anodic aluminum oxide nanopores.

PubMed

Chekmenev, Eduard Y; Hu, Jun; Gor'kov, Peter L; Brey, William W; Cross, Timothy A; Ruuge, Andres; Smirnov, Alex I

2005-04-01

This communication reports the first example of a high resolution solid-state 15N 2D PISEMA NMR spectrum of a transmembrane peptide aligned using hydrated cylindrical lipid bilayers formed inside nanoporous anodic aluminum oxide (AAO) substrates. The transmembrane domain SSDPLVVA(A-15N)SIIGILHLILWILDRL of M2 protein from influenza A virus was reconstituted in hydrated 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine bilayers that were macroscopically aligned by a conventional micro slide glass support or by the AAO nanoporous substrate. 15N and 31P NMR spectra demonstrate that both the phospholipids and the protein transmembrane domain are uniformly aligned in the nanopores. Importantly, nanoporous AAO substrates may offer several advantages for membrane protein alignment in solid-state NMR studies compared to conventional methods. Specifically, higher thermal conductivity of aluminum oxide is expected to suppress thermal gradients associated with inhomogeneous radio frequency heating. Another important advantage of the nanoporous AAO substrate is its excellent accessibility to the bilayer surface for exposure to solute molecules. Such high accessibility achieved through the substrate nanochannel network could facilitate a wide range of structure-function studies of membrane proteins by solid-state NMR.

Cells exposed to nanosecond electrical pulses exhibit biomarkers of mechanical stress

NASA Astrophysics Data System (ADS)

Roth, Caleb C.; Barnes, Ronald A.; Ibey, Bennett L.; Beier, Hope T.; Moen, Erick K.; Glickman, Randolph D.

2015-03-01

Exposure of cells to very short (<1 μs) electric pulses in the megavolt/meter range have been shown to cause disruption of the plasma membrane. This disruption is often characterized by the formation of numerous small pores (<2 nm in diameter) in the plasma membrane that last for several minutes, allowing the flow of ions into the cell. These small pores are called nanopores and the resulting damage to the plasma membrane is referred to as nanoporation. Nanosecond electrical pulse (nsEP) exposure can impart many different stressors on a cell, including electrical, electro-chemical, and mechanical stress. Thus, nsEP exposure is not a "clean" insult, making determination of the mechanism of nanoporation quite difficult. We hypothesize that nsEP exposure creates acoustic shock waves capable of causing nanoporation. Microarray analysis of primary adult human dermal fibroblasts (HDFa) exposed to nsEP, indicated several genes associated with mechanical stress were selectively upregulated 4 h post exposure. The idea that nanoporation is caused by external mechanical force from acoustic shock waves has, to our knowledge, not been investigated. This work will critically challenge the existing paradigm that nanoporation is caused solely by an electric-field driven event and could provide the basis for a plausible explanation for electroporation.

InGaN Light-Emitting Diodes with an Embedded Nanoporous GaN Distributed Bragg Reflectors.

PubMed

Shiu, Guo-Yi; Chen, Kuei-Ting; Fan, Feng-Hsu; Huang, Kun-Pin; Hsu, Wei-Ju; Dai, Jing-Jie; Lai, Chun-Feng; Lin, Chia-Feng

2016-07-01

InGaN light emitting diodes (LED) structure with an embedded 1/4λ-stack nanoporous-GaN/undoped-GaN distributed Bragg reflectors (DBR) structure have been demonstrated. Si-heavily doped GaN epitaxial layers (n(+)-GaN) in the 12-period n(+)-GaN/u-GaN stack structure are transformed into low refractive index nanoporous GaN structure through the doping-selective electrochemical wet etching process. The central wavelength of the nanoporous DBR structure was located at 442.3 nm with a 57 nm linewidth and a 97.1% peak reflectivity. The effective cavity length (6.0λ), the effective penetration depth (278 nm) in the nanoporous DBR structure, and InGaN active layer matching to Fabry-Pérot mode order 12 were observed in the far-field photoluminescence radiative spectra. High electroluminescence emission intensity and line-width narrowing effect were measured in the DBR-LED compared with the non-treated LED structure. Non-linear emission intensity and line-width reducing effect, from 11.8 nm to 0.73 nm, were observed by increasing the laser excited power. Resonant cavity effect was observed in the InGaN LED with bottom nanoporous-DBR and top GaN/air interface.

InGaN Light-Emitting Diodes with an Embedded Nanoporous GaN Distributed Bragg Reflectors

PubMed Central

Shiu, Guo-Yi; Chen, Kuei-Ting; Fan, Feng-Hsu; Huang, Kun-Pin; Hsu, Wei-Ju; Dai, Jing-Jie; Lai, Chun-Feng; Lin, Chia-Feng

2016-01-01

InGaN light emitting diodes (LED) structure with an embedded 1/4λ-stack nanoporous-GaN/undoped-GaN distributed Bragg reflectors (DBR) structure have been demonstrated. Si-heavily doped GaN epitaxial layers (n+-GaN) in the 12-period n+-GaN/u-GaN stack structure are transformed into low refractive index nanoporous GaN structure through the doping-selective electrochemical wet etching process. The central wavelength of the nanoporous DBR structure was located at 442.3 nm with a 57 nm linewidth and a 97.1% peak reflectivity. The effective cavity length (6.0λ), the effective penetration depth (278 nm) in the nanoporous DBR structure, and InGaN active layer matching to Fabry-Pérot mode order 12 were observed in the far-field photoluminescence radiative spectra. High electroluminescence emission intensity and line-width narrowing effect were measured in the DBR-LED compared with the non-treated LED structure. Non-linear emission intensity and line-width reducing effect, from 11.8 nm to 0.73 nm, were observed by increasing the laser excited power. Resonant cavity effect was observed in the InGaN LED with bottom nanoporous-DBR and top GaN/air interface. PMID:27363290

Biomimetic novel nanoporous niobium oxide coating for orthopaedic applications

NASA Astrophysics Data System (ADS)

Pauline, S. Anne; Rajendran, N.

2014-01-01

Niobium oxide was synthesized by sol-gel methodology and a crystalline, nanoporous and adherent coating of Nb2O5 was deposited on 316L SS using the spin coating technique and heat treatment. The synthesis conditions were optimized to obtain a nanoporous morphology. The coating was characterized using attenuated total reflectance-Infrared spectroscopy (ATR-IR), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), atomic force microscopy (AFM) and transmission electron microscopy (TEM) and the formation of crystalline Nb2O5 coating with nanoporous morphology was confirmed. Mechanical studies confirmed that the coating has excellent adherence to the substrate and the hardness value of the coating was excellent. Contact angle analysis showed increased hydrophilicity for the coated substrate. In vitro bioactivity test confirmed that the Nb2O5 coating with nanoporous morphology facilitated the growth of hydroxyapatite (HAp). This was further confirmed by the solution analysis test where increased uptake of calcium and phosphorous ions from simulated body fluid (SBF) was observed. Electrochemical evaluation of the coating confirmed that the crystalline coating is insulative and protective in nature and offered excellent corrosion protection to 316L SS. Thus, this study confirmed that the nanoporous crystalline Nb2O5 coating conferred bioactivity and enhanced corrosion resistance on 316L SS.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media.

PubMed

Huber, Patrick

2015-03-18

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Theoretical models for electrochemical impedance spectroscopy and local ζ-potential of unfolded proteins in nanopores

NASA Astrophysics Data System (ADS)

Vitarelli, Michael J.; Talaga, David S.

2013-09-01

Single solid-state nanopores find increasing use for electrical detection and/or manipulation of macromolecules. These applications exploit the changes in signals due to the geometry and electrical properties of the molecular species found within the nanopore. The sensitivity and resolution of such measurements are also influenced by the geometric and electrical properties of the nanopore. This paper continues the development of an analytical theory to predict the electrochemical impedance spectra of nanopores by including the influence of the presence of an unfolded protein using the variable topology finite Warburg impedance model previously published by the authors. The local excluded volume of, and charges present on, the segment of protein sampled by the nanopore are shown to influence the shape and peak frequency of the electrochemical impedance spectrum. An analytical theory is used to relate the capacitive response of the electrical double layer at the surface of the protein to both the charge density at the protein surface and the more commonly measured zeta potential. Illustrative examples show how the theory predicts that the varying sequential regions of surface charge density and excluded volume dictated by the protein primary structure may allow for an impedance-based approach to identifying unfolded proteins.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

NASA Astrophysics Data System (ADS)

Huber, Patrick

2015-03-01

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Boosting infrared energy transfer in 3D nanoporous gold antennas.

PubMed

Garoli, D; Calandrini, E; Bozzola, A; Ortolani, M; Cattarin, S; Barison, S; Toma, A; De Angelis, F

2017-01-05

The applications of plasmonics to energy transfer from free-space radiation to molecules are currently limited to the visible region of the electromagnetic spectrum due to the intrinsic optical properties of bulk noble metals that support strong electromagnetic field confinement only close to their plasma frequency in the visible/ultraviolet range. In this work, we show that nanoporous gold can be exploited as a plasmonic material for the mid-infrared region to obtain strong electromagnetic field confinement, co-localized with target molecules into the nanopores and resonant with their vibrational frequency. The effective optical response of the nanoporous metal enables the penetration of optical fields deep into the nanopores, where molecules can be loaded thus achieving a more efficient light-matter coupling if compared to bulk gold. In order to realize plasmonic resonators made of nanoporous gold, we develop a nanofabrication method based on polymeric templates for metal deposition and we obtain antenna arrays resonating at mid-infrared wavelengths selected by design. We then coat the antennas with a thin (3 nm) silica layer acting as the target dielectric layer for optical energy transfer. We study the strength of the light-matter coupling at the vibrational absorption frequency of silica at 1240 cm -1 through the analysis of the experimental Fano lineshape that is benchmarked against identical structures made of bulk gold. The boost in the optical energy transfer from free-space mid-infrared radiation to molecular vibrations in nanoporous 3D nanoantenna arrays can open new application routes for plasmon-enhanced physical-chemical reactions.

Co-delivery of ibuprofen and gentamicin from nanoporous anodic titanium dioxide layers.

PubMed

Pawlik, Anna; Jarosz, Magdalena; Syrek, Karolina; Sulka, Grzegorz D

2017-04-01

Although single-drug therapy may prove insufficient in treating bacterial infections or inflammation after orthopaedic surgeries, complex therapy (using both an antibiotic and an anti-inflammatory drug) is thought to address the problem. Among drug delivery systems (DDSs) with prolonged drug release profiles, nanoporous anodic titanium dioxide (ATO) layers on Ti foil are very promising. In the discussed research, ATO samples were synthesized via a three-step anodization process in an ethylene glycol-based electrolyte with fluoride ions. The third step lasted 2, 5 and 10min in order to obtain different thicknesses of nanoporous layers. Annealing the as-prepared amorphous layers at the temperature of 400°C led to obtaining the anatase phase. In this study, water-insoluble ibuprofen and water-soluble gentamicin were used as model drugs. Three different drug loading procedures were applied. The desorption-desorption-diffusion (DDD) model of the drug release was fitted to the experimental data. The effects of crystalline structure, depth of TiO 2 nanopores and loading procedure on the drug release profiles were examined. The duration of the drug release process can be easily altered by changing the drug loading sequence. Water-soluble gentamicin is released for a long period of time if gentamicin is loaded in ATO as the first drug. Additionally, deeper nanopores and anatase phase suppress the initial burst release of drugs. These results confirm that factors such as morphological and crystalline structure of ATO layers, and the procedure of drug loading inside nanopores, allow to alter the drug release performance of nanoporous ATO layers. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of thermal conduction in symmetric and asymmetric nanoporous structures

NASA Astrophysics Data System (ADS)

Yu, Ziqi; Ferrer-Argemi, Laia; Lee, Jaeho

2017-12-01

Nanoporous structures with a critical dimension comparable to or smaller than the phonon mean free path have demonstrated significant thermal conductivity reductions that are attractive for thermoelectric applications, but the presence of various geometric parameters complicates the understanding of governing mechanisms. Here, we use a ray tracing technique to investigate phonon boundary scattering phenomena in Si nanoporous structures of varying pore shapes, pore alignments, and pore size distributions, and identify mechanisms that are primarily responsible for thermal conductivity reductions. Our simulation results show that the neck size, or the smallest distance between nearest pores, is the key parameter in understanding nanoporous structures of varying pore shapes and the same porosities. When the neck size and the porosity are both identical, asymmetric pore shapes provide a lower thermal conductivity compared with symmetric pore shapes, due to localized heat fluxes. Asymmetric nanoporous structures show possibilities of realizing thermal rectification even with fully diffuse surface boundaries, in which optimal arrangements of triangular pores show a rectification ratio up to 13 when the injection angles are optimally controlled. For symmetric nanoporous structures, hexagonal-lattice pores achieve larger thermal conductivity reductions than square-lattice pores due to the limited line of sight for phonons. We also show that nanoporous structures of alternating pore size distributions from large to small pores yield a lower thermal conductivity compared with those of uniform pore size distributions in the given porosity. These findings advance the understanding of phonon boundary scattering phenomena in complex geometries and enable optimal designs of artificial nanostructures for thermoelectric energy harvesting and solid-state cooling systems.

Asymmetric Nanopore Electrode-Based Amplification for Electron Transfer Imaging in Live Cells.

PubMed

Ying, Yi-Lun; Hu, Yong-Xu; Gao, Rui; Yu, Ru-Jia; Gu, Zhen; Lee, Luke P; Long, Yi-Tao

2018-04-25

Capturing real-time electron transfer, enzyme activity, molecular dynamics, and biochemical messengers in living cells is essential for understanding the signaling pathways and cellular communications. However, there is no generalizable method for characterizing a broad range of redox-active species in a single living cell at the resolution of cellular compartments. Although nanoelectrodes have been applied in the intracellular detection of redox-active species, the fabrication of nanoelectrodes to maximize the signal-to-noise ratio of the probe remains challenging because of the stringent requirements of 3D fabrication. Here, we report an asymmetric nanopore electrode-based amplification mechanism for the real-time monitoring of NADH in a living cell. We used a two-step 3D fabrication process to develop a modified asymmetric nanopore electrode with a diameter down to 90 nm, which allowed for the detection of redox metabolism in living cells. Taking advantage of the asymmetric geometry, the above 90% potential drop at the two terminals of the nanopore electrode converts the faradaic current response into an easily distinguishable bubble-induced transient ionic current pattern. Therefore, the current signal was amplified by at least 3 orders of magnitude, which was dynamically linked to the presence of trace redox-active species. Compared to traditional wire electrodes, this wireless asymmetric nanopore electrode exhibits a high signal-to-noise ratio by increasing the current resolution from nanoamperes to picoamperes. The asymmetric nanopore electrode achieves the highly sensitive and selective probing of NADH concentrations as low as 1 pM. Moreover, it enables the real-time nanopore monitoring of the respiration chain (i.e., NADH) in a living cell and the evaluation of the effects of anticancer drugs in an MCF-7 cell. We believe that this integrated wireless asymmetric nanopore electrode provides promising building blocks for the future imaging of electron transfer dynamics in live cells.

[Effects of different annealing conditions on the photoluminescence of nanoporous alumina film].

PubMed

Xie, Ning; Ma, Kai-Di; Shen, Yi-Fan; Wang, Qian

2013-12-01

The nanoporous alumina films were prepared by two-step anodic oxidation in 0.5 mol L-1 oxalic acid electrolyte at 40 V. Photoluminescence (PL) of nanoporous alumina films was investigated under different annealing atmosphere and different temperature. The authors got three results about the PL measurements. In the same annealing atmosphere, when the annealling temperature T< or =600 degreeC, the intensity of the PL peak increases with elevated annealing temperature and reaches a maximum value at 500 degreeC, but the intensity decreases with a further increase in the annealing temperature, and the PL peak intensity of samples increases with the increase in the annealing temperature when the annealling temperature T> or =800 degreeC. In the different annealling atmosphere, the change in the photoluminescence peak position for nanoporous alumina films with the increase in the annealing temperature is different: With the increase in the annealling temperature, the PL peak position for the samples annealed in air atmosphere is blue shifted, while the PL peak position for the samples annealed in vacuum atmosphere will not change. The PL spectra of nanoporous alumina films annealed at 1100 degreeC in air atmosphere can be de-convoluted by three Gaussian components at an excitation wavelength of 350 nm, with bands centered at 387, 410 and 439 nm, respectively. These results suggest that there might be three luminescence centers for the PL of annealed alumina films. At the same annealling temperature, the PL peak intensity of samples annealed in air atmosphere is stronger than that annealed in the vacuum. Based on the experimental results and the X-ray dispersive energy spectrum (EDS) combined with infrared reflect spectra, the luminescence mechanisms of nanoporous alumina films are discussed. There are three luminescence centers in the annealed nanoporous alumina films, which originate from the F center, F+ center and the center associated with the oxalic impurities. The effects of different annealing conditions on the photoluminescence of nanoporous alumina film are reasonably explained.

Nanoporous Au structures by dealloying Au/Ag thermal- or laser-dewetted bilayers on surfaces

NASA Astrophysics Data System (ADS)

Ruffino, F.; Torrisi, V.; Grillo, R.; Cacciato, G.; Zimbone, M.; Piccitto, G.; Grimaldi, M. G.

2017-03-01

Nanoporous Au attracts great technological interest and it is a promising candidate for optical and electrochemical sensors. In addition to nanoporous Au leafs and films, recently, interest was focused on nanoporous Au micro- and nano-structures on surfaces. In this work we report on the study of the characteristics of nanoporous Au structures produced on surfaces. We developed the following procedures to fabricate the nanoporous Au structures: we deposited thin Au/Ag bilayers on SiO2 or FTO (fluorine-doped tin oxide) substrates with thickness xAu and xAg of the Au and Ag layers; we induced the alloying and dewetting processes of the bilayers by furnace annealing processes of the bilayers deposited on SiO2 and by laser irradiations of the bilayers deposited on FTO; the alloying and dewetting processes result in the formation of AuxAgy alloy sub-micron particles being x and y tunable by xAu and xAg. These particles are dealloyed in HNO3 solution to remove the Ag atoms. We obtain, so, nanoporous sub-micron Au particles on the substrates. Analyzing the characteristics of these particles we find that: a) the size and shape of the particles depend on the nature of the dewetting process (solid-state dewetting on SiO2, molten-state dewetting on FTO); b) the porosity fraction of the particles depends on how the alloying process is reached: about 32% of porosity for the particles fabricated by the furnace annealing at 900 °C, about 45% of porosity for the particles fabricated by the laser irradiation at 0.5 J/cm2, in both cases independently on the Ag concentration in the alloy; c) After the dealloying process the mean volume of the Au particles shrinks of about 39%; d) After an annealing at 400 °C the nanoporous Au particles reprise their initial volume while the porosity fraction is reduced. Arguments to justify these behaviors are presented.

Organized energetic composites based on micro and nanostructures and methods thereof

DOEpatents

Gash, Alexander E.; Han, Thomas Yong-Jin; Sirbuly, Donald J.

2012-09-04

An ordered energetic composite structure according to one embodiment includes an ordered array of metal fuel portions; and an oxidizer in gaps located between the metal fuel portions. An ordered energetic composite structure according to another embodiment includes at least one metal fuel portion having an ordered array of nanopores; and an oxidizer in the nanopores. A method for forming an ordered energetic composite structure according to one embodiment includes forming an ordered array of metal fuel portions; and depositing an oxidizer in gaps located between the metal fuel portions. A method for forming an ordered energetic composite structure according to another embodiment includes forming an ordered array of nanopores in at least one metal fuel portion; and depositing an oxidizer in the nanopores.

Protein sequencing via nanopore based devices: a nanofluidics perspective

NASA Astrophysics Data System (ADS)

Chinappi, Mauro; Cecconi, Fabio

2018-05-01

Proteins perform a huge number of central functions in living organisms, thus all the new techniques allowing their precise, fast and accurate characterization at single-molecule level certainly represent a burst in proteomics with important biomedical impact. In this review, we describe the recent progresses in the developing of nanopore based devices for protein sequencing. We start with a critical analysis of the main technical requirements for nanopore protein sequencing, summarizing some ideas and methodologies that have recently appeared in the literature. In the last sections, we focus on the physical modelling of the transport phenomena occurring in nanopore based devices. The multiscale nature of the problem is discussed and, in this respect, some of the main possible computational approaches are illustrated.

Nanoscale Dynamics of Joule heating and Bubble Nucleation in a Solid-State Nanopore

PubMed Central

Levine, Edlyn V.; Burns, Michael M.; Golovchenko, Jene A.

2016-01-01

We present a mathematical model for Joule heating of an electrolytic solution in a nanopore. The model couples the electrical and thermal dynamics responsible for rapid and extreme superheating of the electrolyte within the nanopore. The model is implemented numerically with a finite element calculation, yielding a time and spatially resolved temperature distribution in the nanopore region. Temperatures near the thermodynamic limit of superheat are predicted to be attained just before the explosive nucleation of a vapor bubble is observed experimentally. Knowledge of this temperature distribution enables the evaluation of related phenomena including bubble nucleation kinetics, relaxation oscillation, and bubble dynamics. PACS numbers 47.55.dp, 47.55.db, 85.35.-p, 05.70Fh PMID:26871171

Ion-sculpting of nanopores in amorphous metals, semiconductors, and insulators

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, H. Bola; Madi, Charbel S.; Aziz, Michael J.

2010-06-28

We report the closure of nanopores to single-digit nanometer dimensions by ion sculpting in a range of amorphous materials including insulators (SiO{sub 2} and SiN), semiconductors (a-Si), and metallic glasses (Pd{sub 80}Si{sub 20})--the building blocks of a single-digit nanometer electronic device. Ion irradiation of nanopores in crystalline materials (Pt and Ag) does not cause nanopore closure. Ion irradiation of c-Si pores below 100 deg. C and above 600 deg. C, straddling the amorphous-crystalline dynamic transition temperature, yields closure at the lower temperature but no mass transport at the higher temperature. Ion beam nanosculpting appears to be restricted to materials thatmore » either are or become amorphous during ion irradiation.« less

Improving scattering layer through mixture of nanoporous spheres and nanoparticles in ZnO-based dye-sensitized solar cells.

PubMed

Kim, Chohui; Choi, Hongsik; Kim, Jae Ik; Lee, Sangheon; Kim, Jinhyun; Lee, Woojin; Hwang, Taehyun; Kang, Suji; Moon, Taeho; Park, Byungwoo

2014-01-01

A scattering layer is utilized by mixing nanoporous spheres and nanoparticles in ZnO-based dye-sensitized solar cells. Hundred-nanometer-sized ZnO spheres consisting of approximately 35-nm-sized nanoparticles provide not only effective light scattering but also a large surface area. Furthermore, ZnO nanoparticles are added to the scattering layer to facilitate charge transport and increase the surface area as filling up large voids. The mixed scattering layer of nanoparticles and nanoporous spheres on top of the nanoparticle-based electrode (bilayer geometry) improves solar cell efficiency by enhancing both the short-circuit current (J sc) and fill factor (FF), compared to the layer consisting of only nanoparticles or nanoporous spheres.

Detecting a single molecule using a micropore-nanopore hybrid chip

PubMed Central

2013-01-01

Nanopore-based DNA sequencing and biomolecule sensing have attracted more and more attention. In this work, novel sensing devices were built on the basis of the chips containing nanopore arrays in polycarbonate (PC) membranes and micropores in Si3N4 films. Using the integrated chips, the transmembrane ionic current induced by biomolecule's translocation was recorded and analyzed, which suggested that the detected current did not change linearly as commonly expected with increasing biomolecule concentration. On the other hand, detailed translocation information (such as translocation gesture) was also extracted from the discrete current blockages in basic current curves. These results indicated that the nanofluidic device based on the chips integrated by micropores and nanopores possessed comparative potentials in biomolecule sensing. PMID:24261484

Detecting a single molecule using a micropore-nanopore hybrid chip.

PubMed

Liu, Lei; Zhu, Lizhong; Ni, Zhonghua; Chen, Yunfei

2013-11-21

Nanopore-based DNA sequencing and biomolecule sensing have attracted more and more attention. In this work, novel sensing devices were built on the basis of the chips containing nanopore arrays in polycarbonate (PC) membranes and micropores in Si3N4 films. Using the integrated chips, the transmembrane ionic current induced by biomolecule's translocation was recorded and analyzed, which suggested that the detected current did not change linearly as commonly expected with increasing biomolecule concentration. On the other hand, detailed translocation information (such as translocation gesture) was also extracted from the discrete current blockages in basic current curves. These results indicated that the nanofluidic device based on the chips integrated by micropores and nanopores possessed comparative potentials in biomolecule sensing.

Nanoporous cerium oxide thin film for glucose biosensor.

PubMed

Saha, Shibu; Arya, Sunil K; Singh, S P; Sreenivas, K; Malhotra, B D; Gupta, Vinay

2009-03-15

Nanoporous cerium oxide (CeO(2)) thin film deposited onto platinum (Pt) coated glass plate using pulsed laser deposition (PLD) has been utilized for immobilization of glucose oxidase (GOx). Atomic force microscopy studies reveal the formation of nanoporous surface morphology of CeO(2) thin film. Response studies carried out using differential pulsed voltammetry (DPV) and optical measurements show that the GOx/CeO(2)/Pt bio-electrode shows linearity in the range of 25-300 mg/dl of glucose concentration. The low value of Michaelis-Menten constant (1.01 mM) indicates enhanced enzyme affinity of GOx to glucose. The observed results show promising application of the nanoporous CeO(2) thin film for glucose sensing application without any surface functionalization or mediator.

Solid-state nanopore localization by controlled breakdown of selectively thinned membranes

NASA Astrophysics Data System (ADS)

Carlsen, Autumn T.; Briggs, Kyle; Hall, Adam R.; Tabard-Cossa, Vincent

2017-02-01

We demonstrate precise positioning of nanopores fabricated by controlled breakdown (CBD) on solid-state membranes by spatially varying the electric field strength with localized membrane thinning. We show 100 × 100 nm2 precision in standard SiN x membranes (30-100 nm thick) after selective thinning by as little as 25% with a helium ion beam. Control over nanopore position is achieved through the strong dependence of the electric field-driven CBD mechanism on membrane thickness. Confinement of pore formation to the thinned region of the membrane is confirmed by TEM imaging and by analysis of DNA translocations. These results enhance the functionality of CBD as a fabrication approach and enable the production of advanced nanopore devices for single-molecule sensing applications.

Efficient Fabrication of Nanoporous Si and Si/Ge Enabled by a Heat Scavenger in Magnesiothermic Reactions

PubMed Central

Luo, Wei; Wang, Xingfeng; Meyers, Colin; Wannenmacher, Nick; Sirisaksoontorn, Weekit; Lerner, Michael M.; Ji, Xiulei

2013-01-01

Magnesiothermic reduction can directly convert SiO2 into Si nanostructures. Despite intense efforts, efficient fabrication of highly nanoporous silicon by Mg still remains a significant challenge due to the exothermic reaction nature. By employing table salt (NaCl) as a heat scavenger for the magnesiothermic reduction, we demonstrate an effective route to convert diatom (SiO2) and SiO2/GeO2 into nanoporous Si and Si/Ge composite, respectively. Fusion of NaCl during the reaction consumes a large amount of heat that otherwise collapses the nano-porosity of products and agglomerates silicon domains into large crystals. Our methodology is potentially competitive for a practical production of nanoporous Si-based materials. PMID:23860418

Towards the Ultimate Membranes: Two-dimensional Nanoporous Materials and Films.

PubMed

Agrawal, Kumar Varoon

2018-05-30

The energy-efficient separation of molecules has been a popular topic in chemistry and chemical engineering as a consequence of the large energy-footprint of separation processes in the chemical industry. The Laboratory of Advanced Separations (LAS) at EPFL, led by Prof. Kumar Varoon Agrawal, is focused to develop next-generation, high-performance membranes that can improve the energy efficiency of hydrogen purification, carbon capture, hydrocarbon and water purification. For this, LAS is seeking to develop the ultimate nanoporous membranes, those with a thickness of 1 nm and possessing an array of size-selective nanopores. In this article, the research activities at LAS, especially in the bottom-up and top-down synthesis of chemically and thermally stable, nanoporous two-dimensional materials and membranes are discussed.

Efficient fabrication of nanoporous si and Si/Ge enabled by a heat scavenger in magnesiothermic reactions.

PubMed

Luo, Wei; Wang, Xingfeng; Meyers, Colin; Wannenmacher, Nick; Sirisaksoontorn, Weekit; Lerner, Michael M; Ji, Xiulei

2013-01-01

Magnesiothermic reduction can directly convert SiO2 into Si nanostructures. Despite intense efforts, efficient fabrication of highly nanoporous silicon by Mg still remains a significant challenge due to the exothermic reaction nature. By employing table salt (NaCl) as a heat scavenger for the magnesiothermic reduction, we demonstrate an effective route to convert diatom (SiO2) and SiO2/GeO2 into nanoporous Si and Si/Ge composite, respectively. Fusion of NaCl during the reaction consumes a large amount of heat that otherwise collapses the nano-porosity of products and agglomerates silicon domains into large crystals. Our methodology is potentially competitive for a practical production of nanoporous Si-based materials.

21 CFR 175.210 - Acrylate ester copolymer coating.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylate ester copolymer coating. 175.210 Section... COATINGS Substances for Use as Components of Coatings § 175.210 Acrylate ester copolymer coating. Acrylate...) The acrylate ester copolymer is a fully polymerized copolymer of ethyl acrylate, methyl methacrylate...

Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

DOEpatents

Russell, Thomas P.; Hong, Sung Woo; Lee, Doug Hyun; Park, Soojin; Xu, Ting

2015-10-13

A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

Method of forming oriented block copolymer line patterns, block copolymer line patterns formed thereby, and their use to form patterned articles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russell, Thomas P.; Hong, Sung Woo; Lee, Dong Hyun

A block copolymer film having a line pattern with a high degree of long-range order is formed by a method that includes forming a block copolymer film on a substrate surface with parallel facets, and annealing the block copolymer film to form an annealed block copolymer film having linear microdomains parallel to the substrate surface and orthogonal to the parallel facets of the substrate. The line-patterned block copolymer films are useful for the fabrication of magnetic storage media, polarizing devices, and arrays of nanowires.

Hydrogen-bonded aggregates in precise acid copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lueth, Christopher A.; Bolintineanu, Dan S.; Stevens, Mark J., E-mail: msteve@sandia.gov

2014-02-07

We perform atomistic molecular dynamics simulations of melts of four precise acid copolymers, two poly(ethylene-co-acrylic acid) (PEAA) copolymers, and two poly(ethylene-co-sulfonic acid) (PESA) copolymers. The acid groups are spaced by either 9 or 21 carbons along the polymer backbones. Hydrogen bonding causes the acid groups to form aggregates. These aggregates give rise to a low wavevector peak in the structure factors, in agreement with X-ray scattering data for the PEAA materials. The structure factors for the PESA copolymers are very similar to those for the PEAA copolymers, indicating a similar distance between aggregates which depends on the spacer length butmore » not on the nature of the acid group. The PEAA copolymers are found to form more dimers and other small aggregates than do the PESA copolymers, while the PESA copolymers have both more free acid groups and more large aggregates.« less

Tailoring charge density and hydrogen bonding of imidazolium copolymers for efficient gene delivery.

PubMed

Allen, Michael H; Green, Matthew D; Getaneh, Hiwote K; Miller, Kevin M; Long, Timothy E

2011-06-13

Conventional free radical polymerization with subsequent postpolymerization modification afforded imidazolium copolymers with controlled charge density and side chain hydroxyl number. Novel imidazolium-containing copolymers where each permanent cation contained one or two adjacent hydroxyls allowed precise structure-transfection efficiency studies. The degree of polymerization was identical for all copolymers to eliminate the influence of molecular weight on transfection efficiency. DNA binding, cytotoxicity, and in vitro gene transfection in African green monkey COS-7 cells revealed structure-property-transfection relationships for the copolymers. DNA gel shift assays indicated that higher charge densities and hydroxyl concentrations increased DNA binding. As the charge density of the copolymers increased, toxicity of the copolymers also increased; however, as hydroxyl concentration increased, cytotoxicity remained constant. Changing both charge density and hydroxyl levels in a systematic fashion revealed a dramatic influence on transfection efficiency. Dynamic light scattering of the polyplexes, which were composed of copolymer concentrations required for the highest luciferase expression, showed an intermediate DNA-copolymer binding affinity. Our studies supported the conclusion that cationic copolymer binding affinity significantly impacts overall transfection efficiency of DNA delivery vehicles, and the incorporation of hydroxyl sites offers a less toxic and effective alternative to more conventional highly charged copolymers.

Some properties of electrolyte solutions in nanoconfinement revealed by the measurement of transient filtration potential after pressure switch off.

PubMed

Yaroshchuk, Andriy E; Boiko, Yuriy P; Makovetskiy, Alexandre L

2005-08-16

We have demonstrated that with a composite nanoporous ceramic membrane in a batch membrane cell it is technically feasible to switch off the trans-membrane hydrostatic pressure difference within tens of milliseconds. That enabled us to resolve practically the whole time evolution of transient filtration potential. Measurements of the latter have been complemented by measurements of steady-state salt rejection by the composite membrane and by measurements of the streaming potential and hydraulic permeability of membrane supports available separately. A theory has been developed in terms of network thermodynamics for the electrical response of a bilayer membrane to a pressure perturbation. In combination with the results of salt rejection measurements, from the time transients of filtration potential we could determine the ion transport numbers within the nanoporous layer. Besides that, from the dependence of steady-state salt rejection on the trans-membrane volume flow, we have determined the diffusion permeability of and the salt reflection coefficient in the nanoporous layer. This has enabled us to estimate the contributions of Donnan and non-Donnan mechanisms to the rejection of ions by the nanoporous membrane used in this study. It has been unexpectedly found that the Donnan exclusion played only a secondary role. Our hypothesis is that the non-Donnan exclusion of ions from the nanopores might be caused by changes in water properties in nanoconfinement. Proceeding from the results of steady-state filtration experiments with the membrane and the support, we also concluded that the nanoporous layer was imperfection-free and had a quite narrow pore size distribution, which made it a suitable object for fundamental studies of ion transfer mechanisms in nanopores.

Asymmetric nanopore membranes: Single molecule detection and unique transport properties

NASA Astrophysics Data System (ADS)

Bishop, Gregory William

Biological systems rely on the transport properties of transmembrane channels. Such pores can display selective transport by allowing the passage of certain ions or molecules while rejecting others. Recent advances in nanoscale fabrication have allowed the production of synthetic analogs of such channels. Synthetic nanopores (pores with a limiting dimension of 1--100 nm) can be produced in a variety of materials by several different methods. In the Martin group, we have been exploring the track-etch method to produce asymmetric nanopores in thin films of polymeric or crystalline materials. Asymmetric nanopores are of particular interest due to their ability to serve as ion-current rectifiers. This means that when a membrane that contains such a pore or collection of pores is used to separate identical portions of electrolyte solution, the magnitude of the ionic current will depend not only on the magnitude of the applied potential (as expected) but also the polarity. Ion-current rectification is characterized by an asymmetric current--potential response. Here, the interesting transport properties of asymmetric nanopores (ion-current rectification and the related phenomenon of electroosmotic flow rectification) are explored. The effects of pore shape and pore density on these phenomena are investigated. Membranes that contain a single nanopore can serve as platforms for the single-molecule sensing technique known as resistive pulse sensing. The resistive-pulse sensing method is based on the Coulter principle. Thus, the selectivity of the technique is based largely upon size, making the analysis of mixtures by this method difficult in many cases. Here, the surface of a single nanopore membrane is modified with a molecular recognition agent in an attempt to obtain a more selective resistive-pulse sensor for a specific analyte.

de novo assembly and population genomic survey of natural yeast isolates with the Oxford Nanopore MinION sequencer.

PubMed

Istace, Benjamin; Friedrich, Anne; d'Agata, Léo; Faye, Sébastien; Payen, Emilie; Beluche, Odette; Caradec, Claudia; Davidas, Sabrina; Cruaud, Corinne; Liti, Gianni; Lemainque, Arnaud; Engelen, Stefan; Wincker, Patrick; Schacherer, Joseph; Aury, Jean-Marc

2017-02-01

Oxford Nanopore Technologies Ltd (Oxford, UK) have recently commercialized MinION, a small single-molecule nanopore sequencer, that offers the possibility of sequencing long DNA fragments from small genomes in a matter of seconds. The Oxford Nanopore technology is truly disruptive; it has the potential to revolutionize genomic applications due to its portability, low cost, and ease of use compared with existing long reads sequencing technologies. The MinION sequencer enables the rapid sequencing of small eukaryotic genomes, such as the yeast genome. Combined with existing assembler algorithms, near complete genome assemblies can be generated and comprehensive population genomic analyses can be performed. Here, we resequenced the genome of the Saccharomyces cerevisiae S288C strain to evaluate the performance of nanopore-only assemblers. Then we de novo sequenced and assembled the genomes of 21 isolates representative of the S. cerevisiae genetic diversity using the MinION platform. The contiguity of our assemblies was 14 times higher than the Illumina-only assemblies and we obtained one or two long contigs for 65 % of the chromosomes. This high contiguity allowed us to accurately detect large structural variations across the 21 studied genomes. Because of the high completeness of the nanopore assemblies, we were able to produce a complete cartography of transposable elements insertions and inspect structural variants that are generally missed using a short-read sequencing strategy. Our analyses show that the Oxford Nanopore technology is already usable for de novo sequencing and assembly; however, non-random errors in homopolymers require polishing the consensus using an alternate sequencing technology. © The Author 2017. Published by Oxford University Press.

de novo assembly and population genomic survey of natural yeast isolates with the Oxford Nanopore MinION sequencer

PubMed Central

Istace, Benjamin; Friedrich, Anne; d'Agata, Léo; Faye, Sébastien; Payen, Emilie; Beluche, Odette; Caradec, Claudia; Davidas, Sabrina; Cruaud, Corinne; Liti, Gianni; Lemainque, Arnaud; Engelen, Stefan; Wincker, Patrick; Schacherer, Joseph

2017-01-01

Abstract Background: Oxford Nanopore Technologies Ltd (Oxford, UK) have recently commercialized MinION, a small single-molecule nanopore sequencer, that offers the possibility of sequencing long DNA fragments from small genomes in a matter of seconds. The Oxford Nanopore technology is truly disruptive; it has the potential to revolutionize genomic applications due to its portability, low cost, and ease of use compared with existing long reads sequencing technologies. The MinION sequencer enables the rapid sequencing of small eukaryotic genomes, such as the yeast genome. Combined with existing assembler algorithms, near complete genome assemblies can be generated and comprehensive population genomic analyses can be performed. Results: Here, we resequenced the genome of the Saccharomyces cerevisiae S288C strain to evaluate the performance of nanopore-only assemblers. Then we de novo sequenced and assembled the genomes of 21 isolates representative of the S. cerevisiae genetic diversity using the MinION platform. The contiguity of our assemblies was 14 times higher than the Illumina-only assemblies and we obtained one or two long contigs for 65 % of the chromosomes. This high contiguity allowed us to accurately detect large structural variations across the 21 studied genomes. Conclusion: Because of the high completeness of the nanopore assemblies, we were able to produce a complete cartography of transposable elements insertions and inspect structural variants that are generally missed using a short-read sequencing strategy. Our analyses show that the Oxford Nanopore technology is already usable for de novo sequencing and assembly; however, non-random errors in homopolymers require polishing the consensus using an alternate sequencing technology. PMID:28369459

In Situ Fabrication of PtCo Alloy Embedded in Nitrogen-Doped Graphene Nanopores as Synergistic Catalyst for Oxygen Reduction Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Xing; Wang, Lei; Zhou, Hu

A novel PtCo alloy in situ etched and embedded in graphene nanopores (PtCo/NPG) as a high-performance catalyst for ORR was reported. Graphene nanopores were fabricated in situ while forming PtCo nanoparticles that were uniformly embedded in the graphene nanopores. Given the synergistic effect between PtCo alloy and nanopores, PtCo/NPG exhibited 11.5 times higher mass activity than that of the commercial Pt/C cathode electrocatalyst. DFT calculations indicated that the nanopores in NPG cannot only stabilize PtCo nanoparticles but can also definitely change the electronic structures, thereby change its adsorption abilities. This enhancement can lead to a favorable reaction pathway on PtCo/NPGmore » for ORR. This study showed that PtCo/NPG is a potential candidate for the next generation of Pt-based catalysts in fuel cells. This study also offered a promising alternative strategy and enabled the fabrication of various kinds of metal/graphene nanopore nanohybrids with potential applications in catalysts and potential use for other technological devices. The authors acknowledge the financial support from the National Basic Research Program (973 program, No. 2013CB733501), Zhejiang Provincial Education Department Research Program (Y201326554) and the National Natural Science Foundation of China (No. 21306169, 21101137, 21136001, 21176221 and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC).« less

Fabrication and characterization of a flow-through nanoporous gold nanowire/AAO composite membrane.

PubMed

Liu, L; Lee, W; Huang, Z; Scholz, R; Gösele, U

2008-08-20

The fabrication of a composite membrane of nanoporous gold nanowires and anodic aluminum oxide (AAO) is demonstrated by the electrodeposition of Au-Ag alloy nanowires into an AAO membrane, followed by selective etching of silver from the alloy nanowires. This composite membrane is advantageous for flow-through type catalytic reactions. The morphology evolution of the nanoporous gold nanowires as a function of the diameter of the Au-Ag nanowire 'precursors' is also investigated.

Solid-State Nanopore.

PubMed

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-20

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Solid-State Nanopore

NASA Astrophysics Data System (ADS)

Yuan, Zhishan; Wang, Chengyong; Yi, Xin; Ni, Zhonghua; Chen, Yunfei; Li, Tie

2018-02-01

Solid-state nanopore has captured the attention of many researchers due to its characteristic of nanoscale. Now, different fabrication methods have been reported, which can be summarized into two broad categories: "top-down" etching technology and "bottom-up" shrinkage technology. Ion track etching method, mask etching method chemical solution etching method, and high-energy particle etching and shrinkage method are exhibited in this report. Besides, we also discussed applications of solid-state nanopore fabrication technology in DNA sequencing, protein detection, and energy conversion.

Multilevel description of the DNA molecule translocation in solid-state synthetic nanopores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nosik, V. L., E-mail: v-nosik@yandex.ru; Rudakova, E. B.

2016-07-15

Interest of researchers in micro- and nanofluidics of polymer solutions and, in particular, DNA ionic solutions is constantly increasing. The use of DNA translocation with a controlled velocity through solid-state nanopores and pulsed X-ray beams in new sequencing schemes opens up new possibilities for studying the structure of DNA and other biopolymers. The problems related to the description of DNA molecular motion in a limited volume of nanopore are considered.

Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase

DOE PAGES

Dou, Jian; Tang, Yu; Nguyen, Luan; ...

2016-12-22

Nanoporous gold with minor silver content has been identified as a new type of gold based catalyst for selective oxidation of cyclohexene with molecular oxygen in liquid. By oxidation of the leached nanoporous gold foils in ozone, the minor silver content was oxidized in this paper to form silver oxide nanoclusters on the surface of nanoporous gold. With further treatment in methanol, the surface silver oxide was reduced and surface alloy was formed on gold ligaments. Both nanoporous gold treated with ozone only and the one with ozone and then methanol are very active for selective oxidation of cyclohexene withmore » molecular oxygen in liquid of cyclohexene with a turn-over-frequency (TOF) of 0.55–0.99 molecules per surface Au atom per second under a solvent-free and initiator- free condition. The total selectivity for production of 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was increased from 57.5 % to 80.8 % by an additional treatment of nanoporous gold in methanol after activation in zone. Finally, the correlation of catalytic selectivity for the production of the three products and corresponding surface chemistry of ligament suggests that (1) the formed Au–Ag alloy surface is favorable for the formation of 2-cyclohexen-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide and (2) the surface silver oxide is favorable for the production of cyclohexenyl hydroperoxide.« less

Oxidation of Cyclohexene Catalyzed by Nanoporous Au(Ag) in Liquid Phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Jian; Tang, Yu; Nguyen, Luan

Nanoporous gold with minor silver content has been identified as a new type of gold based catalyst for selective oxidation of cyclohexene with molecular oxygen in liquid. By oxidation of the leached nanoporous gold foils in ozone, the minor silver content was oxidized in this paper to form silver oxide nanoclusters on the surface of nanoporous gold. With further treatment in methanol, the surface silver oxide was reduced and surface alloy was formed on gold ligaments. Both nanoporous gold treated with ozone only and the one with ozone and then methanol are very active for selective oxidation of cyclohexene withmore » molecular oxygen in liquid of cyclohexene with a turn-over-frequency (TOF) of 0.55–0.99 molecules per surface Au atom per second under a solvent-free and initiator- free condition. The total selectivity for production of 2-cyclohexene-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide was increased from 57.5 % to 80.8 % by an additional treatment of nanoporous gold in methanol after activation in zone. Finally, the correlation of catalytic selectivity for the production of the three products and corresponding surface chemistry of ligament suggests that (1) the formed Au–Ag alloy surface is favorable for the formation of 2-cyclohexen-1-one, 2-cyclohexene-1-ol, and cyclohexene oxide and (2) the surface silver oxide is favorable for the production of cyclohexenyl hydroperoxide.« less

Enhanced piezoelectric output of NiO/nanoporous GaN by suppression of internal carrier screening

NASA Astrophysics Data System (ADS)

Waseem, Aadil; Jeong, Dae Kyung; Johar, Muhammad Ali; Kang, Jin-Ho; Ha, Jun-Seok; Key Lee, June; Ryu, Sang-Wan

2018-06-01

The efficiency of piezoelectric nanogenerators (PNGs) significantly depends on the free carrier concentration of semiconductors. In the presence of a mechanical stress, piezoelectric charges are generated at both ends of the PNG, which are rapidly screened by the free carriers. The screening effect rapidly decreases the piezoelectric output within fractions of a second. In this study, the piezoelectric outputs of bulk- and nanoporous GaN-based heterojunction PNGs are compared. GaN thin films were epitaxially grown on sapphire substrates using metal organic chemical vapor deposition. Nanoporous GaN was fabricated using electrochemical etching, depleted of free carriers owing to the surface Fermi-level pinning. A highly resistive NiO thin film was deposited on bulk- and nanoporous GaN using radio frequency magnetron sputter. The NiO/nanoporous GaN PNG (NPNG) under a periodic compressive stress of 4 MPa exhibited an output voltage and current of 0.32 V and 1.48 μA cm‑2, respectively. The output voltage and current of the NiO/thin film-GaN PNG (TPNG) were three and five times smaller than those of the NPNG, respectively. Therefore, the high-resistivity of NiO and nanoporous GaN depleted by the Fermi-level pinning are advantageous and provide a better piezoelectric performance of the NPNG, compared with that of the TPNG.

Size-dependent nonlinear bending of micro/nano-beams made of nanoporous biomaterials including a refined truncated cube cell

NASA Astrophysics Data System (ADS)

Sahmani, S.; Aghdam, M. M.

2017-12-01

Morphology and pore size plays an essential role in the mechanical properties as well as the associated biological capability of a porous structure made of biomaterials. The objective of the current study is to predict the Young's modulus and Poisson's ratio of nanoporous biomaterials including refined truncated cube cells based on a hyperbolic shear deformable beam model. Analytical relationships for the mechanical properties of nanoporous biomaterials are given as a function of the refined cell's dimensions. After that, the size dependency in the nonlinear bending behavior of micro/nano-beams made of such nanoporous biomaterials is analyzed using the nonlocal strain gradient elasticity theory. It is assumed that the micro/nano-beam has one movable end under axial compression in conjunction with a uniform distributed lateral load. The Galerkin method together with an improved perturbation technique is employed to propose explicit analytical expression for nonlocal strain gradient load-deflection curves of the micro/nano-beams made of nanoporous biomaterials subjected to uniform transverse distributed load. It is found that through increment of the pore size, the micro/nano-beam will undergo much more deflection corresponding to a specific distributed load due to the reduction in the stiffness of nanoporous biomaterial. This pattern is more prominent for lower value of applied axial compressive load at the free end of micro/nano-beam.

Structural Integrity of Proteins under Applied Bias during Solid-State Nanopore Translocation

NASA Astrophysics Data System (ADS)

Hasan, Mohammad R.; Khanzada, Raja Raheel; Mahmood, Mohammed A. I.; Ashfaq, Adnan; Iqbal, Samir M.

2015-03-01

The translocation behavior of proteins through solid-state nanopores can be used as a new way to detect and identify proteins. The ionic current through a nanopore that flows under applied bias gets perturbed when a biomolecule traverses the Nanopore. It is important for a protein detection scheme to know of any changes in the three-dimensional structure of the molecule during the process. Here we report the data on structural integrity of protein during translocation through nanopore under different applied biases. Nanoscale Molecular Dynamic was used to establish a framework to study the changes in protein structures as these travelled across the nanopore. The analysis revealed the contributions of structural changes of protein to its ionic current signature. As a model, thrombin protein crystalline structure was imported and positioned inside a 6 nm diameter pore in a 6 nm thick silicon nitride membrane. The protein was solvated in 1 M KCl at 295 K and the system was equilibrated for 20 ns to attain its minimum energy state. The simulation was performed at different electric fields from 0 to 1 kCal/(mol.Å.e). RMSD, radial distribution function, movement of the center of mass and velocity of the protein were calculated. The results showed linear increments in the velocity and perturbations in ionic current profile with increasing electric potential. Support Acknowledged from NSF through ECCS-1201878.

21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

Molecular architecture of electroactive and biodegradable copolymers composed of polylactide and carboxyl-capped aniline trimer.

PubMed

Guo, Baolin; Finne-Wistrand, Anna; Albertsson, Ann-Christine

2010-04-12

Two-, four-, and six-armed branched copolymers with electroactive and biodegradable properties were synthesized by coupling reactions between poly(l-lactides) (PLLAs) with different architecture and carboxyl-capped aniline trimer (CCAT). The aniline oligomer CCAT was prepared from amino-capped aniline trimer and succinic anhydride. FT-IR, NMR, and SEC analyses confirmed the structure of the branched copolymers. UV-vis spectra and cyclic voltammetry of CCAT and copolymer solution showed good electroactive properties, similar to those of polyaniline. The water contact angle of the PLLAs was the highest, followed by the undoped copolymer and the doped copolymers. The values of doped four-armed copolymers were 54-63 degrees . Thermal properties of the polymers were studied by DSC and TGA. The copolymers had better thermal stability than the pure PLLAs, and the T(g) between 48-58 degrees C and T(m) between 146-177 degrees C of the copolymers were lower than those of the pure PLLA counterparts. This kind of electroactive and biodegradable copolymer has a great potential for applications in cardiovascular or neuronal tissue engineering.

Novel spider-web-like nanoporous networks based on jute cellulose nanowhiskers.

PubMed

Cao, Xinwang; Wang, Xianfeng; Ding, Bin; Yu, Jianyong; Sun, Gang

2013-02-15

Cellulose nanowhiskers as a kind of renewable and biocompatible nanomaterials evoke much interest because of its versatility in various applications. Herein, for the first time, a novel controllable fabrication of spider-web-like nanoporous networks based on jute cellulose nanowhiskers (JCNs) deposited on the electrospun (ES) nanofibrous membrane by simple directly immersion-drying method is reported. Jute cellulose nanowhiskers were extracted from jute fibers with a high yield (over 80%) via a 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)/NaBr/NaClO system selective oxidization combined with mechanical homogenization. The morphology of JCNs nanoporous networks/ES nanofibrous membrane architecture, including coverage rate, pore-width and layer-by-layer packing structure of the nanoporous networks, can be finely controlled by regulating the JCNs dispersions properties and drying conditions. The versatile nanoporous network composites based on jute cellulose nanowhiskers with ultrathin diameters (3-10 nm) and nanofibrous membrane supports with diameters of 100-300 nm, would be particularly useful for filter applications. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Power generation by a pH-regulated conical nanopore through reverse electrodialysis

NASA Astrophysics Data System (ADS)

Hsu, Jyh-Ping; Lin, Sheng-Chang; Lin, Chih-Yuan; Tseng, Shiojenn

2017-10-01

To assess the possibility of energy harvesting through reverse electrodialysis (RED), we consider the electrokinetic behavior of the ion transport in a pH-regulated conical nanopore connecting two large reservoirs having different bulk salt concentrations, taking account of the effect of osmotic flow. In particular, we examine the influence of the ion diffusion direction, the solution pH, and the bulk concentration ratio on that behavior in detail, and discuss the underlying mechanisms. We show that the geometrically asymmetric nature of the nanopore yields profound and interesting phenomena arising mainly from the distribution of ions in its interior. Assuming a single polymeric nanopore, a power density of 18.2 W/m2 can be generated. We show that the present system has the potential of serving as an ion-selective and a salinity gradient power generation device. The maximum power efficiency which is based on assuming a linear ionic distribution in nanopore can yield appreciable deviation, especially if pH deviates significantly from 7, where the presence of H+ and OH- needs be considered.

Ion transport and selectivity in biomimetic nanopores with pH-tunable zwitterionic polyelectrolyte brushes.

PubMed

Zeng, Zhenping; Yeh, Li-Hsien; Zhang, Mingkan; Qian, Shizhi

2015-10-28

Inspired by nature, functionalized nanopores with biomimetic structures have attracted growing interests in using them as novel platforms for applications of regulating ion and nanoparticle transport. To improve these emerging applications, we study theoretically for the first time the ion transport and selectivity in short nanopores functionalized with pH tunable, zwitterionic polyelectrolyte (PE) brushes. In addition to background salt ions, the study takes into account the presence of H(+) and OH(-) ions along with the chemistry reactions between functional groups on PE chains and protons. Due to ion concentration polarization, the charge density of PE layers is not homogeneously distributed and depends significantly on the background salt concentration, pH, grafting density of PE chains, and applied voltage bias, thereby resulting in many interesting and unexpected ion transport phenomena in the nanopore. For example, the ion selectivity of the biomimetic nanopore can be regulated from anion-selective (cation-selective) to cation-selective (anion-selective) by diminishing (raising) the solution pH when a sufficiently small grafting density of PE chains, large voltage bias, and low background salt concentration are applied.

Confining metal-halide perovskites in nanoporous thin films

PubMed Central

Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

2017-01-01

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

Modification of electrical properties of silicon dioxide through intrinsic nano-patterns

NASA Astrophysics Data System (ADS)

Majee, Subimal; Barshilia, Devesh; Banerjee, Debashree; Kumar, Sanjeev; Mishra, Prabhash; Akhtar, Jamil

2018-05-01

The inherent network of nanopores and voids in silicon dioxide (SiO2) is generally undesirable for aspects of film quality, electrical insulation and dielectric performance. However, if we view these pores as natural nano-patterns embedded in a dielectric matrix then that opens up new vistas for exploration. The nano-pattern platform can be used to tailor electrical, optical, magnetic and mechanical properties of the carrier film. In this article we report the tunable electrical properties of thermal SiO2 thin-film achieved through utilization of the metal-nanopore network where the pores are filled with metallic Titanium (Ti). Without any intentional chemical doping, we have shown that the electrical resistivity of the oxide film can be controlled through physical filling up of the intrinsic oxide nanopores with Ti. The electrical resistivity of the composite film remains constant even after complete removal of the metal from the film surface except the pores. Careful morphological, electrical and structural analyses are carried out to establish that the presence of Ti in the nanopores play a crucial role in the observed conductive nature of the nanoporous film.

Correlation dynamics and enhanced signals for the identification of serial biomolecules and DNA bases.

PubMed

Ahmed, Towfiq; Haraldsen, Jason T; Rehr, John J; Di Ventra, Massimiliano; Schuller, Ivan; Balatsky, Alexander V

2014-03-28

Nanopore-based sequencing has demonstrated a significant potential for the development of fast, accurate, and cost-efficient fingerprinting techniques for next generation molecular detection and sequencing. We propose a specific multilayered graphene-based nanopore device architecture for the recognition of single biomolecules. Molecular detection and analysis can be accomplished through the detection of transverse currents as the molecule or DNA base translocates through the nanopore. To increase the overall signal-to-noise ratio and the accuracy, we implement a new 'multi-point cross-correlation' technique for identification of DNA bases or other molecules on the single molecular level. We demonstrate that the cross-correlations between each nanopore will greatly enhance the transverse current signal for each molecule. We implement first-principles transport calculations for DNA bases surveyed across a multilayered graphene nanopore system to illustrate the advantages of the proposed geometry. A time-series analysis of the cross-correlation functions illustrates the potential of this method for enhancing the signal-to-noise ratio. This work constitutes a significant step forward in facilitating fingerprinting of single biomolecules using solid state technology.

Fabrication of Self-Ordered Nanoporous Alumina with 69-115 nm Interpore Distances in Sulfuric/Oxalic Acid Mixtures by Hard Anodization

NASA Astrophysics Data System (ADS)

Almasi Kashi, Mohammad; Ramazani, Abdolali; Mayamai, Yashar; Noormohammadi, Mohammad

2010-01-01

Well-ordered nanoporous arrays have been obtained using hard anodization of aluminium in oxalic/sulfuric mixture. Various ordered nanoporous alumina films with pore intervals from 69 to 115 nm were fabricated on aluminum by high current anodization approach with various sulfuric concentrations in the oxalic/sulfuric mixture electrolyte under 36-60 V. The sulfuric acid concentration was changed from 0.06 to 0.2 M. Different configurations of the current-time curve are seen to influence the self-ordering of the nanohole arrays. A current density-time curve with exponential oscillating decay configuration is seen to damage the self-ordered array of the nanopores while those with exponential decay under certain conditions cause ordered nanopore arrays. For each electrolyte mixture, the interpore distance was dependent upon the anodization voltages with proportionality constants of almost 2 nm V-1. The porosity of the samples (about 3.5%) follows the porosity rule of HA. Final anodization and increasing voltage rate (rin) as a function of sulfuric acid concentration are the main sources to influence the self-ordering of the samples.

Ultrasound-propelled nanoporous gold wire for efficient drug loading and release.

PubMed

Garcia-Gradilla, Victor; Sattayasamitsathit, Sirilak; Soto, Fernando; Kuralay, Filiz; Yardımcı, Ceren; Wiitala, Devan; Galarnyk, Michael; Wang, Joseph

2014-10-29

Ultrasound (US)-powered nanowire motors based on nanoporous gold segment are developed for increasing the drug loading capacity. The new highly porous nanomotors are characterized with a tunable pore size, high surface area, and high capacity for the drug payload. These nanowire motors are prepared by template membrane deposition of a silver-gold alloy segment followed by dealloying the silver component. The drug doxorubicin (DOX) is loaded within the nanopores via electrostatic interactions with an anionic polymeric coating. The nanoporous gold structure also facilitates the near-infrared (NIR) light controlled release of the drug through photothermal effects. Ultrasound-driven transport of the loaded drug toward cancer cells followed by NIR-light triggered release is illustrated. The incorporation of the nanoporous gold segment leads to a nearly 20-fold increase in the active surface area compared to common gold nanowire motors. It is envisioned that such US-powered nanomotors could provide a new approach to rapidly and efficiently deliver large therapeutic payloads in a target-specific manner. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination by Small-angle X-ray Scattering of Pore Size Distribution in Nanoporous Track-etched Polycarbonate Membranes

NASA Astrophysics Data System (ADS)

Jonas, A. M.; Legras, R.; Ferain, E.

1998-03-01

Nanoporous track-etched membranes with narrow pore size distributions and average pore size diameters tunable from 100 to 1000 Åare produced by the chemical etching of latent tracks in polymer films after irradiation by a beam of accelerated heavy ions. Nanoporous membranes are used for highly demanding filtration purposes, or as templates to obtain metallic or polymeric nanowires (L. Piraux et al., Nucl. Instr. Meth. Phys. Res. 1997, B131, 357). Such applications call for developments in nanopore size characterization techniques. In this respect, we report on the characterization by small-angle X-ray scattering (SAXS) of nanopore size distribution (nPSD) in polycarbonate track-etched membranes. The obtention of nPSD requires inverting an ill-conditioned inhomogeneous equation. We present different numerical routes to overcome the amplification of experimental errors in the resulting solutions, including a regularization technique allowing to obtain the nPSD without a priori knowledge of its shape. The effect of deviations from cylindrical pore shape on the resulting distributions are analyzed. Finally, SAXS results are compared to results obtained by electron microscopy and conductometry.

Gate modulation of proton transport in a nanopore.

PubMed

Mei, Lanju; Yeh, Li-Hsien; Qian, Shizhi

2016-03-14

Proton transport in confined spaces plays a crucial role in many biological processes as well as in modern technological applications, such as fuel cells. To achieve active control of proton conductance, we investigate for the first time the gate modulation of proton transport in a pH-regulated nanopore by a multi-ion model. The model takes into account surface protonation/deprotonation reactions, surface curvature, electroosmotic flow, Stern layer, and electric double layer overlap. The proposed model is validated by good agreement with the existing experimental data on nanopore conductance with and without a gate voltage. The results show that the modulation of proton transport in a nanopore depends on the concentration of the background salt and solution pH. Without background salt, the gated nanopore exhibits an interesting ambipolar conductance behavior when pH is close to the isoelectric point of the dielectric pore material, and the net ionic and proton conductance can be actively regulated with a gate voltage as low as 1 V. The higher the background salt concentration, the lower is the performance of the gate control on the proton transport.

Nanoscale Investigation of Generation 1 PAMAM Dendrimers Interaction with a Protein Nanopore.

PubMed

Asandei, Alina; Ciuca, Andrei; Apetrei, Aurelia; Schiopu, Irina; Mereuta, Loredana; Seo, Chang Ho; Park, Yoonkyung; Luchian, Tudor

2017-07-21

Herein, we describe at uni-molecular level the interactions between poly(amidoamine) (PAMAM) dendrimers of generation 1 and the α-hemolysin protein nanopore, at acidic and neutral pH, and ionic strengths of 0.5 M and 1 M KCl, via single-molecule electrical recordings. The results indicate that kinetics of dendrimer-α-hemolysin reversible interactions is faster at neutral as compared to acidic pH, and we propose as a putative explanation the fine interplay among conformational and rigidity changes on the dendrimer structure, and the ionization state of the dendrimer and the α-hemolysin. From the analysis of the dendrimer's residence time inside the nanopore, we posit that the pH- and salt-dependent, long-range electrostatic interactions experienced by the dendrimer inside the ion-selective α-hemolysin, induce a non-Stokesian diffusive behavior of the analyte inside the nanopore. We also show that the ability of dendrimer molecules to adapt their structure to nanoscopic spaces, and control the flow of matter through the α-hemolysin nanopore, depends non-trivially on the pH- and salt-induced conformational changes of the dendrimer.

Gassmann Theory Applies to Nanoporous Media

NASA Astrophysics Data System (ADS)

Gor, Gennady Y.; Gurevich, Boris

2018-01-01

Recent progress in extraction of unconventional hydrocarbon resources has ignited the interest in the studies of nanoporous media. Since many thermodynamic and mechanical properties of nanoscale solids and fluids differ from the analogous bulk materials, it is not obvious whether wave propagation in nanoporous media can be described using the same framework as in macroporous media. Here we test the validity of Gassmann equation using two published sets of ultrasonic measurements for a model nanoporous medium, Vycor glass, saturated with two different fluids, argon, and n-hexane. Predictions of the Gassmann theory depend on the bulk and shear moduli of the dry samples, which are known from ultrasonic measurements and the bulk moduli of the solid and fluid constituents. The solid bulk modulus can be estimated from adsorption-induced deformation or from elastic effective medium theory. The fluid modulus can be calculated according to the Tait-Murnaghan equation at the solvation pressure in the pore. Substitution of these parameters into the Gassmann equation provides predictions consistent with measured data. Our findings set up a theoretical framework for investigation of fluid-saturated nanoporous media using ultrasonic elastic wave propagation.

Surface-enhanced Raman spectroscopy on laser-engineered ruthenium dye-functionalized nanoporous gold

NASA Astrophysics Data System (ADS)

Schade, Lina; Franzka, Steffen; Biener, Monika; Biener, Jürgen; Hartmann, Nils

2016-06-01

Photothermal processing of nanoporous gold with a microfocused continuous-wave laser at λ = 532 nm provides a facile means in order engineer the pore and ligament size of nanoporous gold. In this report we take advantage of this approach in order to investigate the size-dependence of enhancement effects in surface-enhanced Raman spectroscopy (SERS). Surface structures with laterally varying pore sizes from 25 nm to ≥200 nm are characterized using scanning electron microscopy and then functionalized with N719, a commercial ruthenium complex, which is widely used in dye-sensitized solar cells. Raman spectroscopy reveals the characteristic spectral features of N719. Peak intensities strongly depend on the pore size. Highest intensities are observed on the native support, i.e. on nanoporous gold with pore sizes around 25 nm. These results demonstrate the particular perspectives of laser-fabricated nanoporous gold structures in fundamental SERS studies. In particular, it is emphasized that laser-engineered porous gold substrates represent a very well defined platform in order to study size-dependent effects with high reproducibility and precision and resolve conflicting results in previous studies.

Rectification of nanopores in aprotic solvents--transport properties of nanopores with surface dipoles.

PubMed

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A; Siwy, Zuzanna S

2015-12-07

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li(+) ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.

Hydrothermally formed three-dimensional nanoporous Ni(OH)2 thin-film supercapacitors.

PubMed

Yang, Yang; Li, Lei; Ruan, Gedeng; Fei, Huilong; Xiang, Changsheng; Fan, Xiujun; Tour, James M

2014-09-23

A three-dimensional nanoporous Ni(OH)2 thin-film was hydrothermally converted from an anodically formed porous layer of nickel fluoride/oxide. The nanoporous Ni(OH)2 thin-films can be used as additive-free electrodes for energy storage. The nanoporous layer delivers a high capacitance of 1765 F g(-1) under three electrode testing. After assembly with porous activated carbon in asymmetric supercapacitor configurations, the devices deliver superior supercapacitive performances with capacitance of 192 F g(-1), energy density of 68 Wh kg(-1), and power density of 44 kW kg(-1). The wide working potential window (up to 1.6 V in 6 M aq KOH) and stable cyclability (∼90% capacitance retention over 10,000 cycles) make the thin-film ideal for practical supercapacitor devices.

Elastic properties of protein functionalized nanoporous polymer films

DOE PAGES

Charles T. Black; Wang, Haoyu; Akcora, Pinar

2015-12-16

Retaining the conformational structure and bioactivity of immobilized proteins is important for biosensor designs and drug delivery systems. Confined environments often lead to changes in conformation and functions of proteins. In this study, lysozyme is chemically tethered into nanopores of polystyrene thin films, and submicron pores in poly(methyl methacrylate) films are functionalized with streptavidin. Nanoindentation experiments show that stiffness of streptavidin increases with decreasing submicron pore sizes. Lysozymes in polystyrene nanopores are found to behave stiffer than the submicron pore sizes and still retain their specific bioactivity relative to the proteins on flat surfaces. Lastly, our results show that proteinmore » functionalized ordered nanoporous polystyrene/poly(methyl methacrylate) films present heterogeneous elasticity and can be used to study interactions between free proteins and designed surfaces.« less

Development of a DNA Sensor Based on Nanoporous Pt-Rich Electrodes

NASA Astrophysics Data System (ADS)

Van Hao, Pham; Thanh, Pham Duc; Xuan, Chu Thi; Hai, Nguyen Hoang; Tuan, Mai Anh

2017-06-01

Nanoporous Pt-rich electrodes with 72 at.% Pt composition were fabricated by sputtering a Pt-Ag alloy, followed by an electrochemical dealloying process to selectively etch away Ag atoms. The surface properties of nanoporous membranes were investigated by energy-dispersive x-ray spectroscopy (EDS), scanning electron microscopy (SEM), atomic force microscopy (AFM), a documentation system, and a gel image system (Gel Doc Imager). A single strand of probe deoxyribonucleic acid (DNA) was immobilized onto the electrode surface by physical adsorption. The DNA probe and target hybridization were measured using a lock-in amplifier and an electrochemical impedance spectroscope (EIS). The nanoporous Pt-rich electrode-based DNA sensor offers a fast response time of 3.7 s, with a limit of detection (LOD) of 4.35 × 10-10 M of DNA target.

Electrostatic Interactions between OmpG Nanopore and Analyte Protein Surface Can Distinguish between Glycosylated Isoforms.

PubMed

Fahie, Monifa A; Chen, Min

2015-08-13

The flexible loops decorating the entrance of OmpG nanopore move dynamically during ionic current recording. The gating caused by these flexible loops changes when a target protein is bound. The gating is characterized by parameters including frequency, duration, and open-pore current, and these features combine to reveal the identity of a specific analyte protein. Here, we show that OmpG nanopore equipped with a biotin ligand can distinguish glycosylated and deglycosylated isoforms of avidin by their differences in surface charge. Our studies demonstrate that the direct interaction between the nanopore and analyte surface, induced by the electrostatic attraction between the two molecules, is essential for protein isoform detection. Our technique is remarkably sensitive to the analyte surface, which may provide a useful tool for glycoprotein profiling.

Communication: Molecular-level insights into asymmetric triblock copolymers: Network and phase development

NASA Astrophysics Data System (ADS)

Tallury, Syamal S.; Mineart, Kenneth P.; Woloszczuk, Sebastian; Williams, David N.; Thompson, Russell B.; Pasquinelli, Melissa A.; Banaszak, Michal; Spontak, Richard J.

2014-09-01

Molecularly asymmetric triblock copolymers progressively grown from a parent diblock copolymer can be used to elucidate the phase and property transformation from diblock to network-forming triblock copolymer. In this study, we use several theoretical formalisms and simulation methods to examine the molecular-level characteristics accompanying this transformation, and show that reported macroscopic-level transitions correspond to the onset of an equilibrium network. Midblock conformational fractions and copolymer morphologies are provided as functions of copolymer composition and temperature.

Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells

DOEpatents

Jenekhe, Samson A; Subramaniyan, Selvam; Ahmed, Eilaf; Xin, Hao; Kim, Felix Sunjoo

2014-10-28

The inventions disclosed, described, and/or claimed herein relate to copolymers comprising copolymers comprising electron accepting A subunits that comprise thiazolothiazole, benzobisthiazole, or benzobisoxazoles rings, and electron donating subunits that comprise certain heterocyclic groups. The copolymers are useful for manufacturing organic electronic devices, including transistors and solar cells. The invention also relates to certain synthetic precursors of the copolymers. Methods for making the copolymers and the derivative electronic devices are also described.

Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

DOEpatents

McGrath, James E [Blacksburg, VA; Park, Ho Bum [Austin, TX; Freeman, Benny D [Austin, TX

2011-10-04

The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

2015-10-01

Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems. Electronic supplementary information (ESI) available: Experimental procedures, synthesis, and characterization of molecules 1, 2 and 3. Explanation of the electrochemical method for approximating nanopore diameter. Additional XPS spectra. See DOI: 10.1039/C5NR02939B

Hemocompatibility evaluation in vitro of methoxy polyethyleneglycol-polycaprolactone copolymer solutions.

PubMed

Hu, Qian; Zhang, Yi; Wang, Changyong; Xu, Jiake; Wu, Jianping; Liu, Zonghua; Xue, Wei

2016-03-01

Amphiphilic block copolymer methoxy polyethyleneglycol-polycaprolactone (mPEG-PCL) has attracted interest in the biomedical field, due to its water solubility and biodegradability. Nevertheless, the blood safety of mPEG-PCL copolymers has not been investigated in detail. Because mPEG-PCL copolymers introduced in vivo would inevitably interact with blood tissue, an investigation of possible interactions of mPEG-PCL with key blood components is crucial. We studied the effects of two mPEG-PCL copolymer solutions on blood coagulation, the morphology and lysis of human red blood cells (RBCs), the structure of plasma fibrinogen, complement activation, and platelet aggregation. We found that higher concentrations of the mPEG-PCL copolymers impaired blood clotting, and the copolymers had little impact on the morphology or lysis of RBCs. From the spectroscopy results, the copolymers affected the local microstructure of fibrinogen. The copolymers significantly activated the complement system in a concentration-dependent way. At higher concentrations, the copolymers impaired platelet aggregation, which may have been mediated by an inhibition of the arachidonic acid pathway. These findings provide important information that may be useful for the molecular design and biomedical applications of mPEG-PCL copolymers. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 802-812, 2016. © 2016 Wiley Periodicals, Inc.

Synthesis and Characterization of Stimuli Responsive Block Copolymers, Self-Assembly Behavior and Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Determan, Michael Duane

The central theme of this thesis work is to develop new block copolymer materials for biomedical applications. While there are many reports of stimuli-responsive amphiphilic [19-21] and crosslinked hydrogel materials [22], the development of an in situ gel forming, pH responsive pentablock copolymer is a novel contribution to the field, Figure 1.1 is a sketch of an ABCBA pentablock copolymer. The A blocks are cationic tertiary amine methacrylates blocked to a central Pluronic F127 triblock copolymer. In addition to the prerequisite synthetic and macromolecular characterization of these new materials, the self-assembled supramolecular structures formed by the pentablock were experimentally evaluated.more » This synthesis and characterization process serves to elucidate the important structure property relationships of these novel materials, The pH and temperature responsive behavior of the pentablock copolymer were explored especially with consideration towards injectable drug delivery applications. Future synthesis work will focus on enhancing and tuning the cell specific targeting of DNA/pentablock copolymer polyplexes. The specific goals of this research are: (1) Develop a synthetic route for gel forming pentablock block copolymers with pH and temperature sensitive properties. Synthesis of these novel copolymers is accomplished with ATRP, yielding low polydispersity and control of the block copolymer architecture. Well defined macromolecular characteristics are required to tailor the phase behavior of these materials. (2) Characterize relationship between the size and shape of pentablock copolymer micelles and gel structure and the pH and temperature of the copolymer solutions with SAXS, SANS and CryoTEM. (3) Evaluate the temperature and pH induced phase separation and macroscopic self-assembly phenomenon of the pentablock copolymer. (4) Utilize the knowledge gained from first three goals to design and formulate drug delivery formulations based on the multi-responsive properties of the pentablock copolymer. Demonstrate potential biomedical applications of these materials with in vitro drug release studies from pentablock copolymer hydrogels. The intent of this work is to contribute to the knowledge necessary for further tailoring of these, and other functional block copolymer materials for biomedical applications.« less

Iodinated glycidyl methacrylate copolymer as a radiopaque material for biomedical applications.

PubMed

Dawlee, S; Jayabalan, M

2013-07-01

Polymeric biomaterial was synthesized by copolymerizing 50:50 mol% of monomers, glycidyl methacrylate and methyl methacrylate. Iodine atoms were then grafted to the epoxide groups of glycidyl methacrylate units, rendering the copolymer radiopaque. The percentage weight of iodine in the present copolymer was found to be as high as 23%. The iodinated copolymer showed higher glass transition temperature and thermal stability in comparison with unmodified polymer. Radiographic analysis showed that the copolymer possessed excellent radiopacity. The iodinated copolymer was cytocompatible to L929 mouse fibroblast cells. The in vivo toxicological evaluation by intracutaneous reactivity test of the copolymer extracts has revealed that the material was nontoxic. Subcutaneous implantation of iodinated copolymer in rats has shown that the material was well tolerated. Upon explantation and histological examination, no hemorrhage, infection or necrosis was observed. The samples were found to be surrounded by a vascularized capsule consisting of connective tissue cells. The results indicate that the iodinated copolymer is biocompatible and may have suitable applications as implantable materials.

EDITORIAL: Nanopores—the 'Holey Grail' in nanotechnology research Nanopores—the 'Holey Grail' in nanotechnology research

NASA Astrophysics Data System (ADS)

Demming, Anna

2012-06-01

'Negative space' may be as important in the development of nanomaterials as it is in creating works of art. The term refers to the space around and between objects, an important aspect in artistic composition. In nanotechnology, while nanoposts and nanowires have been assiduously studied and exploited for enhancing the performance of solar cells [1], real-time chemical sensors [2], UV emitters [3] and many other applications, nanopore structures have also yielded important advances in a wide range of fields. In this issue Melnikov, Leburton and Gracheva report on the electrostatic properties of nanopores in a layered semiconductor, and show how they allow a more accurate characterization of DNA than pores in other membranes [4]. Nanoporous materials have been applied to a diverse range of technological challenges. In recognition of its potential in high-efficiency solar cells, Prakasam and colleagues in the US reported the first ever synthesis of self-aligned nanoporous haematite [5]. Haematite is abundant, stable, non-toxic and has a band gap in the visible region and, as their work demonstrates, the photoresponse of nanoporous haematite is very promising for energy harvesting applications. Nanoporous aluminum oxide has also proved to be a particularly valuable material in applications ranging from liquid display panels to biosensor microchips. A collaboration of researchers in Taiwan demonstrated that porous aluminum oxide on an indium tin oxide surface could act as an alignment layer in liquid crystal display panels that have a transmittance of 60-80%, and switch from black to bright with a response time of 62.5 ms [6]. In Korea, Chung, Son and Min investigated the effect of nanostructural parameters of porous aluminum oxide on cell adhesion and proliferation for cell-based microchips [7]. While aluminum oxide without any modifications is not favourable for adherent cell culture, the proliferation of cells dramatically increased in porous aluminum oxide, particularly when the aspect ratio of the nanopore was near unity. In the mid 1990s a collaboration of researchers in the US demonstrated that nanopores could be used to characterize DNA [8]. They showed that as an electric field drove DNA molecules through a pore in a lipid bilayer membrane, the decrease in ionic current due to the partially blocked channel allowed measurement of the polynucleotide length. 'With further improvements, the method could in principle provide direct, high-speed detection of the sequence of bases in single molecules of DNA or RNA', suggested the authors. The idea inspired a catalogue of further research. Gracheva and colleagues in Illinois described a modified approach to detecting DNA using a nanopore in a membrane fabricated from a metal-oxide-semiconductor (MOS) capacitor [9]. The use of semiconductor materials allows the direct integration of high-sensitivity nanoscale MOS amplifiers on the nanopore layer structure to improve the signal. Researchers in the Netherlands have investigated ways of refining geometrical control of nanopores in SiN membranes for more accurate molecular characterization [10]. They reported the fabrication of nanopores using transmission electron microscope beams of different sizes. They found that the stability of small nanopores is related to their geometry, which could be controlled by the size of the beam used in fabrication. One challenge for accurate DNA characterization has been the speed of translocation through the pore. In a collaboration between the University of Illinois and the University of Notre-Dame in Indiana, researchers used a time-varying electric field to slow down the molecule's passage in the pore [11]. In this issue, researchers in Illinois have studied the translocation and stretching of DNA in a pore in a semiconductor membrane consisting of doped p- and n-layers of Si forming a p-n-junction [4]. Control over the stretching of the DNA is important, as is controlling the speed of translocation. Interference between the secondary structure of the probed molecule can interfere with the recorded signal, muddling measurements of the molecule's charge. According to Gracheva and her colleagues, 'the results indicate that the tunable local electric field inside the membrane can effectively control dynamics of a DNA in the channel to either momentarily trap, slow down or allow the biomolecule to translocate at will'. The fertility of research based on nanopores complements well the interest in nanowires and nanoposts. This may largely be a symptom of the comprehensive rigour in scientific enquiry which encourages the investigation of all approaches to a solution. It was once suggested that 'art and science have their meeting point in method' [12]. One might also argue that the creative and inspired ingenuity that is evident in the application of nanopores to such wide-ranging technological challenges demonstrates how the development of scientific methods is in itself a fine art. References [1] Qiu J et al 2010 Solution-derived 40 μm vertically aligned ZnO nanowire arrays as photoelectrodes in dye-sensitized solar cells Nanotechnology 21 195602 [2] Park I, Li Z, Pisano A P and Williams R S 2010 Top-down fabricated silicon nanowire sensors for real-time chemical detection Nanotechnology 21 015501 [3] Gao J et al 2011 UV light emitting transparent conducting tin-doped indium oxide (ITO) nanowires Nanotechnology 22 195706 [4] Melnikov D V, Leburton J-P and Gracheva M E 2012 Slowing down and stretching DNA with an electrically tunable nanopore in a p-n semiconductor membrane Nanotechnology 23 255501 [5] Prakasam H E, Varghese O K, Paulose M, Mor G K and Grimes C A 2006 Synthesis and photoelectrochemical properties of nanoporous iron (III) oxide by potentiostatic anodization Nanotechnology 17 4285-91 [6] Hong C, Tang T-T, Hung C-Y, Pan R-P and Fang W 2010 Liquid crystal alignment in nanoporous anodic aluminum oxide layer for LCD panel applications Nanotechnology 21 285201 [7] Chung S H, Son S J and Min J 2010 The nanostructure effect on the adhesion and growth rates of epithelial cells with well-defined nanoporous alumina s substrates Nanotechnology 21 125104 [8] Kasianowicz J J, Brandin E, Branton D and Deamer D W 1996 Characterization of individual polynucleotide molecules using a membrane channel Proc. Natl Acad. Sci. 93 13770-3 [9] Gracheva M E, Xiong A, Aksimentiev A, Schulten K, Timp G and Leburton J-P 2006 Simulation of the electric response of DNA translocation through a semiconductor nanopore-capacitor Nanotechnology 17 622-33 [10] Van Den Hout M, Hall A R, Wu M Y, Zandbergen H W, Dekker C and Dekker N H 2010 Controlling nanopore size, shape and stability Nanotechnology 21 115304 [11] Mirsaidov U, Comer J, Dimitrov V, Aksimentiev A and Timp G 2010 Slowing the translocation of double-stranded DNA using a nanopore smaller than the double helix Nanotechnology 21 395501 [12] Baron E and Bulwer L L 1864 Caxtoniana vol 2 (Leipzig: Bernard Tauchnits) p 122

Electrochemical Protection of Thin Film Electrodes in Solid State Nanopores

PubMed Central

Harrer, Stefan; Waggoner, Philip S.; Luan, Binquan; Afzali-Ardakani, Ali; Goldfarb, Dario L.; Peng, Hongbo; Martyna, Glenn; Rossnagel, Stephen M.; Stolovitzky, Gustavo A.

2011-01-01

We have eliminated electrochemical surface oxidation and reduction as well as water decomposition inside sub-5-nm wide nanopores in conducting TiN membranes using a surface passivation technique. Nanopore ionic conductances, and therefore pore diameters, were unchanged in passivated pores after applying potentials of ±4.5 V for as long as 24 h. Water decomposition was eliminated by using aqueous 90% glycerol solvent. The use of a protective self-assembled monolayer of hexadecylphosphonic acid was also investigated. PMID:21597142

Controlled growth of ordered nanopore arrays in GaN.

PubMed

Wildeson, Isaac H; Ewoldt, David A; Colby, Robert; Stach, Eric A; Sands, Timothy D

2011-02-09

High-quality, ordered nanopores in semiconductors are attractive for numerous biological, electrical, and optical applications. Here, GaN nanorods with continuous pores running axially through their centers were grown by organometallic vapor phase epitaxy. The porous nanorods nucleate on an underlying (0001)-oriented GaN film through openings in a SiN(x) template that are milled by a focused ion beam, allowing direct placement of porous nanorods. Nanopores with diameters ranging from 20-155 nm were synthesized with crystalline sidewalls.

Tailoring the Nanoporous Architecture of Hydrogels to Exploit Entropic Trapping

NASA Astrophysics Data System (ADS)

Shi, Nan; Ugaz, Victor M.

2010-09-01

Macromolecules embedded in a nanoporous matrix display anomalous transport behavior in the entropic trapping regime. But these phenomena have not been widely explored in hydrogel matrices because it has not been clear how to link them to the underlying heterogeneous nanopore morphology. Here we introduce a theoretical model that establishes this connection and describe microchip DNA electrophoresis experiments that demonstrate how entropic trapping effects can be exploited to yield a trend of increasing resolving power with DNA size (the opposite of what is conventionally observed).

Translocation time of a polymer chain through an energy gradient nanopore

NASA Astrophysics Data System (ADS)

Luo, Meng-Bo; Zhang, Shuang; Wu, Fan; Sun, Li-Zhen

2017-06-01

The translocation time of a polymer chain through an interaction energy gradient nanopore was studied by Monte Carlo simulations and the Fokker-Planck equation with double-absorbing boundary conditions. Both the simulation and calculation revealed three different behaviors for polymer translocation. These behaviors can be explained qualitatively from free-energy landscapes obtained for polymer translocation at different parameters. Results show that the translocation time of a polymer chain through a nanopore can be tuned by suitably designing the interaction energy gradient.

The Upper Limit of Energy Density of Nanoporous Materials Functionalized Liquid

NASA Astrophysics Data System (ADS)

Han, Aijie; Punyamurtula, Venkata K.; Kim, Taewan; Qiao, Yu

2008-06-01

In this article, we report the experimental result of energy dissipation of a mobil crystalline material (MCM) 41 in mercury. The MCM41 contains a large volume fraction of nanometer-sized pores. As the applied pressure is relatively high, the nanopore surfaces are exposed to mercury. Due to the large nanopore surface area and the large solid-liquid interfacial tension, the energy dissipation effectiveness of this system is ultrahigh, representing the upper limit that can be achieved by the pressure-induced infiltration technique.

Nanoporous hard data: optical encoding of information within nanoporous anodic alumina photonic crystals

NASA Astrophysics Data System (ADS)

Santos, Abel; Law, Cheryl Suwen; Pereira, Taj; Losic, Dusan

2016-04-01

Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for developing advanced nanophotonic tools for a wide range of applications, including sensing, photonic tagging, self-reporting drug releasing systems and secure encoding of information.Herein, we present a method for storing binary data within the spectral signature of nanoporous anodic alumina photonic crystals. A rationally designed multi-sinusoidal anodisation approach makes it possible to engineer the photonic stop band of nanoporous anodic alumina with precision. As a result, the transmission spectrum of these photonic nanostructures can be engineered to feature well-resolved and selectively positioned characteristic peaks across the UV-visible spectrum. Using this property, we implement an 8-bit binary code and assess the versatility and capability of this system by a series of experiments aiming to encode different information within the nanoporous anodic alumina photonic crystals. The obtained results reveal that the proposed nanosized platform is robust, chemically stable, versatile and has a set of unique properties for data storage, opening new opportunities for developing advanced nanophotonic tools for a wide range of applications, including sensing, photonic tagging, self-reporting drug releasing systems and secure encoding of information. Electronic supplementary information (ESI) available: Further details about anodisation profiles, SEM cross-section images, digital pictures, transmission spectra, photonic barcodes and ASCII codes of the different NAA photonic crystals fabricated and analysed in our study. See DOI: 10.1039/c6nr01068g

Main-chain supramolecular block copolymers.

PubMed

Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus

2011-01-01

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

Monte Carlo studies on the interfacial properties and interfacial structures of ternary symmetric blends with gradient copolymers.

PubMed

Sun, Dachuan; Guo, Hongxia

2012-08-09

Using Monte Carlo simulation methods, the effects of the comonomer sequence distribution on the interfacial properties (including interfacial tension, interfacial thickness, saturated interfacial area per copolymer, and bending modulus) and interfacial structures (including chain conformations and comonomer distributions of the simulated copolymers at the interfaces) of a ternary symmetric blend containing two immiscible homopolymers and one gradient copolymer are investigated. We find that copolymers with a larger composition gradient width have a broader comonomer distribution along the interface normal, and hence more pronouncedly enlarge the interfacial thickness and reduce the interfacial tension. Furthermore, the counteraction effect, which arises from the tendency of heterogeneous segments in gradient copolymers to phase separate and enter their miscible phases to reduce the local enthalpy, decreases the stretching of copolymers along the interface normal direction. As a result, copolymers with a larger width of gradient composition can occupy a larger interfacial area and form softer monolayers at saturation and are more efficient in facilitating the formation of bicontinuous microemulsions. Additionally, chain length ratio, segregation strength, and interactions between homopolymers and copolymers can alter the interfacial character of gradient copolymers. There exists a strong coupling between the comonomer sequence distribution, chain conformation, and interfacial properties. Especially, bending modulus is mainly determined by the complicated interplay of interfacial copolymer density and interfacial chain conformation.

Formation of nanophases in epoxy thermosets containing amphiphilic block copolymers with linear and star-like topologies.

PubMed

Wang, Lei; Zhang, Chongyin; Cong, Houluo; Li, Lei; Zheng, Sixun; Li, Xiuhong; Wang, Jie

2013-07-11

In this work, we investigated the effect of topological structures of block copolymers on the formation of the nanophase in epoxy thermosets containing amphiphilic block copolymers. Two block copolymers composed of poly(ε-caprolactone) (PCL) and poly(2,2,2-trifluoroethyl acrylate) (PTFEA) blocks were synthesized to possess linear and star-shaped topologies. The star-shaped block copolymer composed a polyhedral oligomeric silsesquioxane (POSS) core and eight poly(ε-caprolactone)-block-poly(2,2,2-trifluoroethyl acrylate) (PCL-b-PTFEA) diblock copolymer arms. Both block copolymers were synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process; they were controlled to have identical compositions of copolymerization and lengths of blocks. Upon incorporating both block copolymers into epoxy thermosets, the spherical PTFEA nanophases were formed in all the cases. However, the sizes of PTFEA nanophases from the star-like block copolymer were significantly lower than those from the linear diblock copolymer. The difference in the nanostructures gave rise to the different glass transition behavior of the nanostructured thermosets. The dependence of PTFEA nanophases on the topologies of block copolymers is interpreted in terms of the conformation of the miscible subchain (viz. PCL) at the surface of PTFEA microdomains and the restriction of POSS cages on the demixing of the thermoset-philic block (viz. PCL).

Distribution of short block copolymer chains in Binary Blends of Block Copolymers Having Hydrogen Bonding

NASA Astrophysics Data System (ADS)

Kwak, Jongheon; Han, Sunghyun; Kim, Jin Kon

2014-03-01

A binary mixture of two block copolymers whose blocks are capable of forming the hydrogen bonding allows one to obtain various microdomains that could not be expected for neat block copolymer. For instance, the binary blend of symmetric polystyrene-block-poly(2-vinylpyridine) copolymer (PS-b-P2VP) and polystyrene-block-polyhydroxystyrene copolymer (PS-b-PHS) blends where the hydrogen bonding occurred between P2VP and PHS showed hexagonally packed (HEX) cylindrical and body centered cubic (BCC) spherical microdomains. To know the exact location of short block copolymer chains at the interface, we synthesized deuterated polystyrene-block-polyhydroxystyrene copolymer (dPS-b-PHS) and prepared a binary mixture with PS-b-P2VP. We investigate, via small angle X-ray scattering (SAXS) and neutron reflectivity (NR), the exact location of shorter dPS block chain near the interface of the microdomains.

Modeling random methyl branching in ethylene/ propylene copolymers using metathesis chemistry: synthesis and thermal behavior.

PubMed

Sworen, John C; Smith, Jason A; Wagener, Kenneth B; Baugh, Lisa S; Rucker, Steven P

2003-02-26

The structure of random ethylene/propylene (EP) copolymers has been modeled using step polymerization chemistry. Six ethylene/propylene model copolymers have been prepared via acyclic diene metathesis (ADMET) polymerization and characterized for primary and higher level structure using in-depth NMR, IR, DSC, WAXD, and GPC analysis. These copolymers possess 1.5, 7.1, 13.6, 25.0, 43.3, and 55.6 methyl branches per 1000 carbons. Examination of these macromolecules by IR and WAXD analysis has demonstrated the first hexagonal phase in EP copolymers containing high ethylene content (90%) without the influence of sample manipulation (temperature, pressure, or radiation). Thermal behavior studies have shown that the melting point and heat of fusion decrease as the branch content increases. Further, comparisons have been made between these random ADMET EP copolymers, random EP copolymers made by typical chain addition techniques, and precisely branched ADMET EP copolymers.

Inhomogeneity of block copolymers at the interface of an immiscible polymer blend

NASA Astrophysics Data System (ADS)

Ryu, Ji Ho; Kim, YongJoo; Lee, Won Bo

2018-04-01

We present the effects of structure and stiffness of block copolymers on the interfacial properties of an immiscible homopolymer blend. Diblock and two-arm grafted copolymers with variation in stiffness are modeled using coarse-grained molecular dynamics to compare the compatibilization efficiency, i.e., reduction of interfacial tension. Overall, grafted copolymers are located more compactly at the interface and show better compatibilization efficiency than diblock copolymers. In addition, an increase in the stiffness for one of the blocks of the diblock copolymers causes unusual inhomogeneous interfacial coverage due to bundle formation. However, an increase in the stiffness for one of blocks of the grafted copolymers prevents the bundle formation due to the branched chain. As a result, homogeneous interfacial coverage of homopolymer blends is realized with significant reduction of interfacial tension which makes grafted copolymer a better candidate for the compatibilizer of immiscible homopolymer blend.

Direct Prototyping of Patterned Nanoporous Carbon: A Route from Materials to On-chip Devices

PubMed Central

Shen, Caiwei; Wang, Xiaohong; Zhang, Wenfeng; Kang, Feiyu

2013-01-01

Prototyping of nanoporous carbon membranes with three-dimensional microscale patterns is significant for integration of such multifunctional materials into various miniaturized systems. Incorporating nano material synthesis into microelectronics technology, we present a novel approach to direct prototyping of carbon membranes with highly nanoporous structures inside. Membranes with significant thicknesses (1 ~ 40 μm) are rapidly prototyped at wafer level by combining nano templating method with readily available microfabrication techniques, which include photolithography, high-temperature annealing and etching. In particular, the high-surface-area membranes are specified as three-dimensional electrodes for micro supercapacitors and show high performance compared to reported ones. Improvements in scalability, compatibility and cost make the general strategy promising for batch fabrication of operational on-chip devices or full integration of three-dimensional nanoporous membranes with existing micro systems. PMID:23887486

Electrokinetic-flow-induced viscous drag on a tethered DNA inside a nanopore.

PubMed

Ghosal, Sandip

2007-12-01

Recent work has shown that the resistive force arising from viscous effects within the pore region could explain observed translocation times in certain experiments involving voltage-driven translocations of DNA through nanopores [Ghosal, Phys. Rev. E 71, 051904 (2006); Phys. Rev. Lett. 98, 238104 (2007)]. The electrokinetic flow inside the pore and the accompanying viscous effects also play a crucial role in the interpretation of experiments where the DNA is immobilized inside a nanopore [Keyser, Nat. Phys. 2, 473 (2006)]. In this paper the viscous force is explicitly calculated for a nanopore of cylindrical geometry. It is found that the reductions of the tether force due to viscous drag and due to charge reduction by Manning condensation are of similar size. The result is of importance in the interpretation of experimental data on tethered DNA.

Optimization of the molecular dynamics method for simulations of DNA and ion transport through biological nanopores.

PubMed

Wells, David B; Bhattacharya, Swati; Carr, Rogan; Maffeo, Christopher; Ho, Anthony; Comer, Jeffrey; Aksimentiev, Aleksei

2012-01-01

Molecular dynamics (MD) simulations have become a standard method for the rational design and interpretation of experimental studies of DNA translocation through nanopores. The MD method, however, offers a multitude of algorithms, parameters, and other protocol choices that can affect the accuracy of the resulting data as well as computational efficiency. In this chapter, we examine the most popular choices offered by the MD method, seeking an optimal set of parameters that enable the most computationally efficient and accurate simulations of DNA and ion transport through biological nanopores. In particular, we examine the influence of short-range cutoff, integration timestep and force field parameters on the temperature and concentration dependence of bulk ion conductivity, ion pairing, ion solvation energy, DNA structure, DNA-ion interactions, and the ionic current through a nanopore.

Investigation of the effect of Anodized Duration toward Photocatalytic Performance of Nb2O5

NASA Astrophysics Data System (ADS)

Sabirin Zoolfakar, Ahmad; Atiqah Mokhtar, Nurul; Rani, Rozina Abdul; Samihah Khairir, Nur; Aqma Abu Talip, Mahzaton; Hafiz Mamat, Mohamad; Kadir, Rosmalini Abdul; Rusop, M.

2018-03-01

Highly oriented Nb2O5 nanoporous network produced via anodization for photocatalytic activity of methyl orange (MO) is presented. The anodization duration was varies from 0.5 to 2 hours and the photocatalytic performance is observed by degradation of MO solution. The Nb2O5 nanoparticles were added in MO solution and were exposed to the solar simulator for 3 hours. The morphology of Nb2O5 nanoporous and the photocatalytic performance are characterized in Field Emission Scanning Electron Microscopy (FESEM) and UV-Vis spectrophotometer, respectively. The result shows that different duration of anodized produce different sizes of nanoporous diameter that will significantly affect the photocatalytic performance. The 1.5 hours of anodized has the largest diameter size of nanoporous and exhibited the best photocatalytic performance

Plasmonic activity on gold nanoparticles embedded in nanopores formed in a surface layer of silica glass by swift-heavy-ion irradiation.

PubMed

Nomura, Ken-ichi; Ohki, Yoshimichi; Fujimaki, Makoto; Wang, Xiaomin; Awazu, Koichi; Komatsubara, Tetsuro

2009-11-25

Silica glass was irradiated by swift heavy ions by selecting the ion species and its energy in order to induce the largest damaged regions. These regions were then selectively etched by hydrofluoric acid vapour to form nanopores on the glass surface. Subsequently, gold nanoparticles were embedded into the nanopores by vacuum evaporation, followed by thermal treatment. In the new plasmonic structure obtained with these procedures, the localized surface plasmon excitation wavelength induced around the gold nanoparticles was found to show a redshift, which agreed well with the theoretical calculation, when water was introduced into the nanopores. This indicates that the fabricated structure can be used as a sensing element to detect the adhesion of substances such as biomolecules to the nanoparticles by measuring the redshift.

Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO2) and adsorption of remazol reactive dye

NASA Astrophysics Data System (ADS)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

2015-09-01

Nanoporous amorphous-MnO2 was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH3COO)2.4H2O) in 0.1 M KMnO4. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO2 bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO2. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO2 showed 99 - 100% decolorization.

Method of fabricating a scalable nanoporous membrane filter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tringe, Joseph W; Balhorn, Rodney L; Zaidi, Saleem

A method of fabricating a nanoporous membrane filter having a uniform array of nanopores etch-formed in a thin film structure (e.g. (100)-oriented single crystal silicon) having a predetermined thickness, by (a) using interferometric lithography to create an etch pattern comprising a plurality array of unit patterns having a predetermined width/diameter, (b) using the etch pattern to etch frustum-shaped cavities or pits in the thin film structure such that the dimension of the frustum floors of the cavities are substantially equal to a desired pore size based on the predetermined thickness of the thin film structure and the predetermined width/diameter ofmore » the unit patterns, and (c) removing the frustum floors at a boundary plane of the thin film structure to expose, open, and thereby create the nanopores substantially having the desired pore size.« less

Highly sensitive detection using microring resonator and nanopores

NASA Astrophysics Data System (ADS)

Bougot-Robin, K.; Hoste, J. W.; Le Thomas, N.; Bienstman, P.; Edel, J. B.

2016-04-01

One of the most significant challenges facing physical and biological scientists is the accurate detection and identification of single molecules in free-solution environments. The ability to perform such sensitive and selective measurements opens new avenues for a large number of applications in biological, medical and chemical analysis, where small sample volumes and low analyte concentrations are the norm. Access to information at the single or few molecules scale is rendered possible by a fine combination of recent advances in technologies. We propose a novel detection method that combines highly sensitive label-free resonant sensing obtained with high-Q microcavities and position control in nanoscale pores (nanopores). In addition to be label-free and highly sensitive, our technique is immobilization free and does not rely on surface biochemistry to bind probes on a chip. This is a significant advantage, both in term of biology uncertainties and fewer biological preparation steps. Through combination of high-Q photonic structures with translocation through nanopore at the end of a pipette, or through a solid-state membrane, we believe significant advances can be achieved in the field of biosensing. Silicon microrings are highly advantageous in term of sensitivity, multiplexing, and microfabrication and are chosen for this study. In term of nanopores, we both consider nanopore at the end of a nanopipette, with the pore being approach from the pipette with nanoprecise mechanical control. Alternatively, solid state nanopores can be fabricated through a membrane, supporting the ring. Both configuration are discussed in this paper, in term of implementation and sensitivity.

Nanopore sequencing in microgravity

PubMed Central

McIntyre, Alexa B R; Rizzardi, Lindsay; Yu, Angela M; Alexander, Noah; Rosen, Gail L; Botkin, Douglas J; Stahl, Sarah E; John, Kristen K; Castro-Wallace, Sarah L; McGrath, Ken; Burton, Aaron S; Feinberg, Andrew P; Mason, Christopher E

2016-01-01

Rapid DNA sequencing and analysis has been a long-sought goal in remote research and point-of-care medicine. In microgravity, DNA sequencing can facilitate novel astrobiological research and close monitoring of crew health, but spaceflight places stringent restrictions on the mass and volume of instruments, crew operation time, and instrument functionality. The recent emergence of portable, nanopore-based tools with streamlined sample preparation protocols finally enables DNA sequencing on missions in microgravity. As a first step toward sequencing in space and aboard the International Space Station (ISS), we tested the Oxford Nanopore Technologies MinION during a parabolic flight to understand the effects of variable gravity on the instrument and data. In a successful proof-of-principle experiment, we found that the instrument generated DNA reads over the course of the flight, including the first ever sequenced in microgravity, and additional reads measured after the flight concluded its parabolas. Here we detail modifications to the sample-loading procedures to facilitate nanopore sequencing aboard the ISS and in other microgravity environments. We also evaluate existing analysis methods and outline two new approaches, the first based on a wave-fingerprint method and the second on entropy signal mapping. Computationally light analysis methods offer the potential for in situ species identification, but are limited by the error profiles (stays, skips, and mismatches) of older nanopore data. Higher accuracies attainable with modified sample processing methods and the latest version of flow cells will further enable the use of nanopore sequencers for diagnostics and research in space. PMID:28725742

Nanoporous Ca3Co4O9 Thin Films for Transferable Thermoelectrics

PubMed Central

2018-01-01

The development of high-performance and transferable thin-film thermoelectric materials is important for low-power applications, e.g., to power wearable electronics, and for on-chip cooling. Nanoporous films offer an opportunity to improve thermoelectric performance by selectively scattering phonons without affecting electronic transport. Here, we report the growth of nanoporous Ca3Co4O9 thin films by a sequential sputtering-annealing method. Ca3Co4O9 is promising for its high Seebeck coefficient and good electrical conductivity and important for its nontoxicity, low cost, and abundance of its constituent raw materials. To grow nanoporous films, multilayered CaO/CoO films were deposited on sapphire and mica substrates by rf-magnetron reactive sputtering from elemental Ca and Co targets, followed by annealing at 700 °C to form the final phase of Ca3Co4O9. This phase transformation is accompanied by a volume contraction causing formation of nanopores in the film. The thermoelectric propoperties of the nanoporous Ca3Co4O9 films can be altered by controlling the porosity. The lowest electrical resistivity is ∼7 mΩ cm, yielding a power factor of 2.32 × 10–4 Wm–1K–2 near room temperature. Furthermore, the films are transferable from the primary mica substrates to other arbitrary polymer platforms by simple dry transfer, which opens an opportunity of low-temperature use these materials. PMID:29905306

Synthesis and Characterization of Comb and Centipede Multigraft Copolymers P nBA- g-PS with High Molecular Weight Using Miniemulsion Polymerization

DOE PAGES

Wang, Wenwen; Wang, Weiyu; Lu, Xinyi; ...

2014-10-23

For this study, comb and centipede multigraft copolymers, poly(n-butyl acrylate)-g-polystyrene (PnBA-g-PS) with PnBA backbones and PS side chains, were synthesized via high-vacuum anionic polymerization and miniemulsion polymerization. Single-tailed and double-tailed PS macromonomers were synthesized by anionic polymerization and Steglich esterification. Subsequently, the copolymerization of each macromonomer and nBA was carried out in miniemulsion, and multigraft copolymers were obtained. The latex particles of multigraft copolymers were characterized using dynamic light scattering. The molecular weights of macromonomers and multigraft copolymers were analyzed by size exclusion chromatography. Moreover, the molecular weights and structures of macromonomers were investigated by matrix-assisted laser desorption/ionization time-of-flight massmore » spectrometry and 1H nuclear magnetic resonance spectroscopy. The weight contents of PS in comb and centipede multigraft copolymers were calculated by 1H nuclear magnetic resonance spectroscopy. The thermal properties of multigraft copolymers were characterized by thermogravimetric analysis and differential scanning calorimetry. The microphase separation of multigraft copolymers was observed by atomic force microscopy and transmission electronic microscopy. Rheological measurements showed that comb and centipede multigraft copolymers have elastic properties when the weight content of PS side chains is 26–32 wt %. Centipede multigraft copolymers possess better elastic properties than comb multigraft copolymers with the similar weight content of PS. In conclusion, these findings are similar to previous results on poly(isoprene-g-polystyrene) comb and centipede copolymers made by anionic polymerization.« less

A novel material screening platform for nanoporous gold-based neural electrodes

NASA Astrophysics Data System (ADS)

Chapman, Christopher Abbott Reece

Neural-electrical interfaces have emerged in the past decades as a promising modality to facilitate the understanding of the electropathophysiology of neurological disorders as well as the normal functioning of the central nervous system, and enable the treatment of neurological defects through electrical stimulation or electrically-controlled drug delivery. However, chronically implanted electrodes face a myriad of design challenges, including their coupling to neural tissue (biocompatibility), small form factor requirement, and their electrical properties (maintaining a low electrical impedance). Planar electrode materials such as planar platinum and gold experience a large increase in electrical impedance when electrode dimensions are reduced to increase spatial resolution of neural recordings. A decrease in electrode surface area reduces the total capacitance of the electrode double layer resulting in an increase in electrode impedance. This high impedance can reduce the signal amplitude and increase the thermal noise, resulting in degradation of signal-to-noise ratio. Conventionally, this increase in electrical impedance at small electrode dimensions has been mitigated by coatings with rough morphologies such as platinum black, conducting polymers, and titanium nitride. Porous surfaces have high effective surface area enabling low impedance at small electrode dimensions. However, achieving long-term stability of cellular coupling to the electrode surface has remained difficult. Designing electrodes that can physically couple with neurons successfully and maintain low impedance at small electrode dimensions necessitates consideration of novel electrode coatings, such as carbon nanotubes and gold nanopillars. Another promising material, and focus of this proposal, is thin film nanoporous gold (np-Au). Nanoporous gold is a promising material for addressing these limitations because of its inherently large effective surface area allows for lower impedances at small form factors, and its modifiable surface morphology can be used to control cell-electrode coupling. Additionally, thin film nanoporous gold is fabricated by traditional microfabrication methods, and thus can be directly adopted by the current state-of-the-art neural electrode fabrication processes. All these properties make thin film nanoporous gold a promising candidate for use in neural electrode surfaces. This dissertation seeks to characterize both the morphological and the electrical response of neural cells to thin film nanoporous gold morphologies using an in vitro electrode morphology screening platform. The specific aims for this proposal are to: (i) develop a electrode morphology library that displays varying topographies to study structure-property relationships of thin film nanoporous gold and cellular response, (ii) characterize neural cell response to identified nanoporous gold topographies that reduce adverse tissue response in vitro, and (iii) develop an electrophysiology platform to characterize neural coupling to each identified nanoporous gold topography.

Hemicellulose block copolymers made from woods for wide-range directed self-assembly lithography enabling wider range of applicable patterning size

NASA Astrophysics Data System (ADS)

Morita, Kazuyo; Yamamoto, Kimiko

2017-03-01

Xylan, one of hemicellulose family, block copolymer was newly developed for wide-range directed self-assembly lithography (DSA). Xylan is higher hydrophilic material because of having many hydroxy groups in one molecule. It means that xylan block copolymer has a possibility of high-chi block copolymer. Generally, DSA is focused on microphase separation for smaller size with high-chi block copolymer and not well known for larger size. In this study, xylan block copolymer was confirmed enabling wider range of patterning size, from smaller size to larger size. The key of xylan block copolymer is a new molecular structure of block copolymer and sugar chain control technology. Sugar content is the important parameter for not only micro-phase separation property but also line edge roughness (LER) and defects. Based on the sugar control technology, wide-range (hp 8.3nm to 26nm L/S and CD 10nm to 51nm hole) DSA patterning was demonstrated. Additionally it was confirmed that xylan block copolymer is suitable for sequential infiltration synthesis (SIS) process.

Bicomponent Block Copolymers Derived from One or More Random Copolymers as an Alternative Route to Controllable Phase Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ashraf, Arman R.; Ryan, Justin J.; Satkowski, Michael M.

Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical- and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, we demonstrate that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks is a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms ofmore » the order-disorder transition (ODT), has been investigated. Our results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that the predicted ODT can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.« less

Cesium-Induced Ionic Conduction through a Single Nanofluidic Pore Modified with Calixcrown Moieties.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Cervera, Javier; Mafe, Salvador; Niemeyer, Christof M; Ensinger, Wolfgang

2017-09-12

We demonstrate experimentally and theoretically a nanofluidic device for the selective recognition of the cesium ion by exploiting host-guest interactions inside confined geometry. For this purpose, a host molecule, i.e., the amine-terminated p-tert-butylcalix[4]arene-crown (t-BuC[4]C-NH 2 ), is successfully synthesized and functionalized on the surface of a single conical nanopore fabricated in a poly(ethylene terephthalate) (PET) membrane through carbodiimide coupling chemistry. On exposure to the cesium cation, the t-BuC[4]C-Cs + complex is formed through host-guest interaction, leading to the generation of positive fixed charges on the pore surface. The asymmetrical distribution of these groups along the conical nanopore leads to the electrical rectification observed in the current-voltage (I-V) curve. On the contrary, other alkali cations are not able to induce any significant change in the rectification characteristics of the nanopore. The success of the chemical modification is monitored from the changes in the electrical readout of the nanopore. Theoretical results based on the Nernst-Planck and Poisson equations further demonstrate the validity of the experimental approach to the cesium-induced ionic conduction of the nanopore.

Structural Inheritance and Redox Performance of Nanoporous Electrodes from Nanocrystalline Fe85.2B10-14P0-4Cu0.8 Alloys

PubMed Central

Fu, Chaoqun; Xu, Lijun; Dan, Zhenhua; Makino, Akihiro; Hara, Nobuyoshi; Qin, Fengxiang; Chang, Hui

2017-01-01

Nanoporous electrodes have been fabricated by selectively dissolving the less noble α-Fe crystalline phase from nanocrystalline Fe85.2B14–xPxCu0.8 alloys (x= 0, 2, 4 at.%). The preferential dissolution is triggered by the weaker electrochemical stability of α-Fe nanocrystals than amorphous phase. The final nanoporous structure is mainly composed of amorphous residual phase and minor undissolved α-Fe crystals and can be predicted from initial microstructure of nanocrystalline precursor alloys. The structural inheritance is proved by the similarity of the size and outlines between nanopores formed after dealloying in 0.1 M H2SO4 and α-Fe nanocrystals precipitated after annealing of amorphous Fe85.2B14−xPxCu0.8 (x = 0, 2, 4 at.%) alloys. The Redox peak current density of the nanoporous electrodes obtained from nanocrystalline Fe85.2B10P4Cu0.8 alloys is more than one order higher than those of Fe plate electrode and its counterpart nanocrystalline alloys due to the large surface area and nearly-amorphous nature of ligaments. PMID:28594378

A cost-effective nanoporous ultrathin film electrode based on nanoporous gold/IrO2 composite for proton exchange membrane water electrolysis

NASA Astrophysics Data System (ADS)

Zeng, Yachao; Guo, Xiaoqian; Shao, Zhigang; Yu, Hongmei; Song, Wei; Wang, Zhiqiang; Zhang, Hongjie; Yi, Baolian

2017-02-01

A cost-effective nanoporous ultrathin film (NPUF) electrode based on nanoporous gold (NPG)/IrO2 composite has been constructed for proton exchange membrane (PEM) water electrolysis. The electrode was fabricated by integrating IrO2 nanoparticles into NPG through a facile dealloying and thermal decomposition method. The NPUF electrode is featured in its 3D interconnected nanoporosity and ultrathin thickness. The nanoporous ultrathin architecture is binder-free and beneficial for improving electrochemical active surface area, enhancing mass transport and facilitating releasing of oxygen produced during water electrolysis. Serving as anode, a single cell performance of 1.728 V (@ 2 A cm-2) has been achieved by NPUF electrode with a loading of IrO2 and Au at 86.43 and 100.0 μg cm-2 respectively, the electrolysis voltage is 58 mV lower than that of conventional electrode with an Ir loading an order of magnitude higher. The electrolysis voltage kept relatively constant up to 300 h (@250 mA cm-2) during the course of durability test, manifesting that NPUF electrode is promising for gas evolution.

Limited Quantum Helium Transportation through Nano-channels by Quantum Fluctuation

PubMed Central

Ohba, Tomonori

2016-01-01

Helium at low temperatures has unique quantum properties such as superfluidity, which causes it to behave differently from a classical fluid. Despite our deep understanding of quantum mechanics, there are many open questions concerning the properties of quantum fluids in nanoscale systems. Herein, the quantum behavior of helium transportation through one-dimensional nanopores was evaluated by measuring the adsorption of quantum helium in the nanopores of single-walled carbon nanohorns and AlPO4-5 at 2–5 K. Quantum helium was transported unimpeded through nanopores larger than 0.7 nm in diameter, whereas quantum helium transportation was significantly restricted through 0.4-nm and 0.6-nm nanopores. Conversely, nitrogen molecules diffused through the 0.4-nm nanopores at 77 K. Therefore, quantum helium behaved as a fluid comprising atoms larger than 0.4–0.6 nm. This phenomenon was remarkable, considering that helium is the smallest existing element with a (classical) size of approximately 0.27 nm. This finding revealed the presence of significant quantum fluctuations. Quantum fluctuation determined the behaviors of quantum flux and is essential to understanding unique quantum behaviors in nanoscale systems. PMID:27363671

Ion transport in sub-5-nm graphene nanopores.

PubMed

Suk, Myung E; Aluru, N R

2014-02-28

Graphene nanopore is a promising device for single molecule sensing, including DNA bases, as its single atom thickness provides high spatial resolution. To attain high sensitivity, the size of the molecule should be comparable to the pore diameter. However, when the pore diameter approaches the size of the molecule, ion properties and dynamics may deviate from the bulk values and continuum analysis may not be accurate. In this paper, we investigate the static and dynamic properties of ions with and without an external voltage drop in sub-5-nm graphene nanopores using molecular dynamics simulations. Ion concentration in graphene nanopores sharply drops from the bulk concentration when the pore radius is smaller than 0.9 nm. Ion mobility in the pore is also smaller than bulk ion mobility due to the layered liquid structure in the pore-axial direction. Our results show that a continuum analysis can be appropriate when the pore radius is larger than 0.9 nm if pore conductivity is properly defined. Since many applications of graphene nanopores, such as DNA and protein sensing, involve ion transport, the results presented here will be useful not only in understanding the behavior of ion transport but also in designing bio-molecular sensors.

Nanoporous Mo2C functionalized 3D carbon architecture anode for boosting flavins mediated interfacial bioelectrocatalysis in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zou, Long; Lu, Zhisong; Huang, Yunhong; Long, Zhong-er; Qiao, Yan

2017-08-01

An efficient microbial electrocatalysis in microbial fuel cells (MFCs) needs both high loading of microbes (biocatalysts) and robust interfacial electron transfer from microbes to electrode. Herein a nanoporous molybdenum carbide (Mo2C) functionalized carbon felt electrode with rich 3D hierarchical porous architecture is applied as MFC anode to achieve superior electrocatalytic performance. The nanoporous Mo2C functionalized anode exhibits strikingly improved microbial electrocatalysis in MFCs with 5-fold higher power density and long-term stability of electricity production. The great enhancement is attributed to the introduction of rough Mo2C nanostructural interface into macroporous carbon architecture for promoting microbial growth with great excretion of endogenous electron shuttles (flavins) and rich available nanopores for enlarging electrochemically active surface area. Importantly, the nanoporous Mo2C functionalized anode is revealed for the first time to have unique electrocatalytic activity towards redox reaction of flavins with more negative redox potential, indicating a more favourable thermodynamic driving force for anodic electron transfer. This work not only provides a promising electrode for high performance MFCs but also brings up a new insight into the effect of nanostructured materials on interfacial bioelectrocatalysis.

Capture and alignment of phi29 viral particles in sub-40 nanometer porous alumina membranes.

PubMed

Moon, Jeong-Mi; Akin, Demir; Xuan, Yi; Ye, Peide D; Guo, Peixuan; Bashir, Rashid

2009-02-01

Bacteriophage phi29 virus nanoparticles and its associated DNA packaging nanomotor can provide for novel possibilities towards the development of hybrid bio-nano structures. Towards the goal of interfacing the phi29 viruses and nanomotors with artificial micro and nanostructures, we fabricated nanoporous Anodic Aluminum Oxide (AAO) membranes with pore size of 70 nm and shrunk the pores to sub 40 nm diameter using atomic layer deposition (ALD) of Aluminum Oxide. We were able to capture and align particles in the anodized nanopores using two methods. Firstly, a functionalization and polishing process to chemically attach the particles in the inner surface of the pores was developed. Secondly, centrifugation of the particles was utilized to align them in the pores of the nanoporous membranes. In addition, when a mixture of empty capsids and packaged particles was centrifuged at specific speeds, it was found that the empty capsids deform and pass through 40 nm diameter pores whereas the particles packaged with DNA were mainly retained at the top surface of the nanoporous membranes. Fluorescence microscopy was used to verify the selective filtration of empty capsids through the nanoporous membranes.

Spontaneous Transport of Single-Stranded DNA through Graphene-MoS2 Heterostructure Nanopores.

PubMed

Luan, Binquan; Zhou, Ruhong

2018-04-24

The effective transport of a single-stranded DNA (ssDNA) molecule through a solid-state nanopore is essential to the future success of high-throughput and low-cost DNA sequencing. Compatible with current electric sensing technologies, here, we propose and demonstrate by molecular dynamics simulations the ssDNA transport through a quasi-two-dimensional nanopore in a heterostructure stacked together with different 2D materials, such as graphene and molybdenum disulfide (MoS 2 ). Due to different chemical potentials, U, of DNA bases on different 2D materials, it is energetically favorable for a ssDNA molecule to move from the low- U MoS 2 surface to the high- U graphene surface through a nanopore. With the proper attraction between the negatively charged phosphate group in each nucleotide and the positively charged Mo atoms exposed on the pore surface, the ssDNA molecule can be temporarily seized and released thereafter through a thermal activation, that is, a slow and possible nucleotide-by-nucleotide transport. A theoretical formulation is then developed for the free energy of the ssDNA transiting a heterostructure nanopore to properly characterize the non-equilibrium stick-slip-like motion of a ssDNA molecule.

Graphene Nanopores for Protein Sequencing.

PubMed

Wilson, James; Sloman, Leila; He, Zhiren; Aksimentiev, Aleksei

2016-07-19

An inexpensive, reliable method for protein sequencing is essential to unraveling the biological mechanisms governing cellular behavior and disease. Current protein sequencing methods suffer from limitations associated with the size of proteins that can be sequenced, the time, and the cost of the sequencing procedures. Here, we report the results of all-atom molecular dynamics simulations that investigated the feasibility of using graphene nanopores for protein sequencing. We focus our study on the biologically significant phenylalanine-glycine repeat peptides (FG-nups)-parts of the nuclear pore transport machinery. Surprisingly, we found FG-nups to behave similarly to single stranded DNA: the peptides adhere to graphene and exhibit step-wise translocation when subject to a transmembrane bias or a hydrostatic pressure gradient. Reducing the peptide's charge density or increasing the peptide's hydrophobicity was found to decrease the translocation speed. Yet, unidirectional and stepwise translocation driven by a transmembrane bias was observed even when the ratio of charged to hydrophobic amino acids was as low as 1:8. The nanopore transport of the peptides was found to produce stepwise modulations of the nanopore ionic current correlated with the type of amino acids present in the nanopore, suggesting that protein sequencing by measuring ionic current blockades may be possible.

Comprehensive study of thin film evaporation from nanoporous membranes for enhanced thermal management

NASA Astrophysics Data System (ADS)

Wilke, Kyle; Barabadi, Banafsheh; Lu, Zhengmao; Zhang, Tiejun; Wang, Evelyn

Performance of emerging electronics is often dictated by the ability to dissipate heat generated in the device. Thin film evaporation from nanopores promises enhanced thermal management by reducing the thermal transport resistance across the liquid film while providing capillary pumping. We present a study of the dependence of evaporation from nanopores on a variety of geometric parameters. Anodic aluminum oxide membranes were used as an experimental template. A biphilic treatment was also used to create a hydrophobic section of the pore to control meniscus location. We demonstrated different heat transfer regimes and observed more than an order of magnitude increase in dissipated heat flux by confining fluid within the nanopore. Pore diameter had little effect on evaporation performance at pore radii of this length scale due to the negligible conduction resistance from the pore wall to the evaporating interface. The dissipated heat flux scaled linearly with porosity as the evaporative area increased. Furthermore, it was demonstrated that moving the meniscus as little as 1 μm into the pore could decrease performance significantly. The results provide a better understanding of evaporation from nanopores and provide guidance in future device design.

Nanolock-Nanopore Facilitated Digital Diagnostics of Cancer Driver Mutation in Tumor Tissue.

PubMed

Wang, Yong; Tian, Kai; Shi, Ruicheng; Gu, Amy; Pennella, Michael; Alberts, Lindsey; Gates, Kent S; Li, Guangfu; Fan, Hongxin; Wang, Michael X; Gu, Li-Qun

2017-07-28

Cancer driver mutations are clinically significant biomarkers. In precision medicine, accurate detection of these oncogenic changes in patients would enable early diagnostics of cancer, individually tailored targeted therapy, and precise monitoring of treatment response. Here we investigated a novel nanolock-nanopore method for single-molecule detection of a serine/threonine protein kinase gene BRAF V600E mutation in tumor tissues of thyroid cancer patients. The method lies in a noncovalent, mutation sequence-specific nanolock. We found that the nanolock formed on the mutant allele/probe duplex can separate the duplex dehybridization procedure into two sequential steps in the nanopore. Remarkably, this stepwise unzipping kinetics can produce a unique nanopore electric marker, with which a single DNA molecule of the cancer mutant allele can be unmistakably identified in various backgrounds of the normal wild-type allele. The single-molecule sensitivity for mutant allele enables both binary diagnostics and quantitative analysis of mutation occurrence. In the current configuration, the method can detect the BRAF V600E mutant DNA lower than 1% in the tumor tissues. The nanolock-nanopore method can be adapted to detect a broad spectrum of both transversion and transition DNA mutations, with applications from diagnostics to targeted therapy.

Fluoride-induced modulation of ionic transport in asymmetric nanopores functionalized with "caged" fluorescein moieties.

PubMed

Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Cervera, Javier; Niemeyer, Christof M; Ensinger, Wolfgang

2016-04-28

We demonstrate experimentally and theoretically a nanofluidic fluoride sensing device based on a single conical pore functionalized with "caged" fluorescein moieties. The nanopore functionalization is based on an amine-terminated fluorescein whose phenolic hydroxyl groups are protected with tert-butyldiphenylsilyl (TBDPS) moieties. The protected fluorescein (Fcn-TBDPS-NH2) molecules are then immobilized on the nanopore surface via carbodiimide coupling chemistry. Exposure to fluoride ions removes the uncharged TBDPS moieties due to the fluoride-promoted cleavage of the silicon-oxygen bond, leading to the generation of negatively charged groups on the fluorescein moieties immobilized onto the pore surface. The asymmetrical distribution of these groups along the conical nanopore leads to the electrical rectification observed in the current-voltage (I-V) curve. On the contrary, other halides and anions are not able to induce any significant ionic rectification in the asymmetric pore. In each case, the success of the chemical functionalization and deprotection reactions is monitored through the changes observed in the I-V curves before and after the specified reaction step. The theoretical results based on the Nernst-Planck and Poisson equations further demonstrate the validity of an experimental approach to fluoride-induced modulation of nanopore current rectification behaviour.

Crystalline imide/arylene ether copolymers

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

1995-01-01

Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends

DOE PAGES

Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

2017-02-07

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary themore » connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.« less

Smart membranes for nitrate removal, water purification, and selective ion transportation

DOEpatents

Wilson, William D [Pleasanton, CA; Schaldach, Charlene M [Pleasanton, CA; Bourcier, William L [Livermore, CA; Paul, Phillip H [Livermore, CA

2009-12-15

A computer designed nanoengineered membrane for separation of dissolved species. One embodiment provides an apparatus for treatment of a fluid that includes ions comprising a microengineered porous membrane, a system for producing an electrical charge across the membrane, and a series of nanopores extending through the membrane. The nanopores have a pore size such that when the fluid contacts the membrane, the nanopores will be in a condition of double layer overlap and allow passage only of ions opposite to the electrical charge across the membrane.

Electrically generated eddies at an eightfold stagnation point within a nanopore

PubMed Central

Sherwood, J. D.; Mao, M.; Ghosal, S.

2014-01-01

Electrically generated flows around a thin dielectric plate pierced by a cylindrical hole are computed numerically. The geometry represents that of a single nanopore in a membrane. When the membrane is uncharged, flow is due solely to induced charge electroosmosis, and eddies are generated by the high fields at the corners of the nanopore. These eddies meet at stagnation points. If the geometry is chosen correctly, the stagnation points merge to form a single stagnation point at which four streamlines cross at a point and eight eddies meet. PMID:25489206

Study on Locally Confined Deposition of Si Nanocrystals in High-Aspect-Ratio Si Nano-Pillar Arrays for Nano-Electronic and Nano-Photonic Applications II

DTIC Science & Technology

2010-12-03

photoluminescence characteristics of equivalent-size controlled silicon quantum dots by employing a nano-porous aluminum oxide membrane as the template for growing...synthesis of Si quantum dots (Si-QDs) embedded in low-temperature (500oC) annealed Si-rich SiOx nano-rod deposited in nano-porous anodic aluminum oxide ...characteristics of the equivalent-size controlled Si-QDs by employing the nano-porous AAO membrane as the template for growing Si-rich SiOx nano-rods

DNA Base-Calling from a Nanopore Using a Viterbi Algorithm

PubMed Central

Timp, Winston; Comer, Jeffrey; Aksimentiev, Aleksei

2012-01-01

Nanopore-based DNA sequencing is the most promising third-generation sequencing method. It has superior read length, speed, and sample requirements compared with state-of-the-art second-generation methods. However, base-calling still presents substantial difficulty because the resolution of the technique is limited compared with the measured signal/noise ratio. Here we demonstrate a method to decode 3-bp-resolution nanopore electrical measurements into a DNA sequence using a Hidden Markov model. This method shows tremendous potential for accuracy (∼98%), even with a poor signal/noise ratio. PMID:22677395

[Prospects for applications in human health of nanopore-based sequencing].

PubMed

Audebert, Christophe; Hot, David; Caboche, Ségolène

2018-04-01

High throughput sequencing has opened up new clinical opportunities moving towards a medicine of precision. Oncology, infectious diseases or human genomics, many applications have been developed in recent years. The introduction of a third generation of nanopore-based sequencing technology, addressing some of the weaknesses of the previous generation, heralds a new revolution. Portability, real time, long reads and marginal investment costs, these promising new technologies point to a new shift of paradigm. What are the perspectives opened up by nanopores for clinical applications? © 2018 médecine/sciences – Inserm.

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Studies on novel radiopaque methyl methacrylate: glycidyl methacrylate based polymer for biomedical applications.

PubMed

Dawlee, S; Jayakrishnan, A; Jayabalan, M

2009-12-01

A new class of radiopaque copolymer using methyl methacrylate (MMA) and glycidyl methacrylate (GMA) monomers was synthesized and characterized. The copolymer was made radiopaque by the epoxide ring opening of GMA using the catalyst o-phenylenediamine and the subsequent covalent attachment of elemental iodine. The copolymer was characterized by Fourier transform infrared (FTIR) spectra, energy dispersive X-ray analysis using environmental scanning electron microscope (EDAX), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). X-ray visibility of the copolymer was checked by X-radiography. Blood compatibility and cytotoxicity of the newly synthesized copolymer were also evaluated. The iodinated copolymer was thermally stable, blood compatible, non-cytotoxic, and highly radiopaque. The presence of bulky iodine group created a new copolymer with modified properties for potential use in biomedical applications.

Periodic nanostructures from self assembled wedge-type block-copolymers

DOEpatents

Xia, Yan; Sveinbjornsson, Benjamin R.; Grubbs, Robert H.; Weitekamp, Raymond; Miyake, Garret M.; Piunova, Victoria; Daeffler, Christopher Scot

2015-06-02

The invention provides a class of wedge-type block copolymers having a plurality of chemically different blocks, at least a portion of which incorporates a wedge group-containing block providing useful properties. For example, use of one or more wedge group-containing blocks in some block copolymers of the invention significantly inhibits chain entanglement and, thus, the present block copolymers materials provide a class of polymer materials capable of efficient molecular self-assembly to generate a range of structures, such as periodic nanostructures and microstructures. Materials of the present invention include copolymers having one or more wedge group-containing blocks, and optionally for some applications copolymers also incorporating one or more polymer side group-containing blocks. The present invention also provides useful methods of making and using wedge-type block copolymers.

Sugar-influenced water diffusion, interaction, and retention in clay interlayer nanopores probed by theoretical simulations and experimental spectroscopies

NASA Astrophysics Data System (ADS)

Aristilde, Ludmilla; Galdi, Stephen M.; Kelch, Sabrina E.; Aoki, Thalia G.

2017-08-01

Understanding the hydrodynamics in clay nanopores is important for gaining insights into the trapping of water, nutrients, and contaminants in natural and engineered soils. Previous investigations have focused on the interlayer organization and molecular diffusion coefficients (D) of cations and water molecules in cation-saturated interlayer nanopores of smectite clays. Little is known, however, about how these interlayer dynamic properties are influenced by the ubiquitous presence of small organic compounds such as sugars in the soil environment. Here we probed the effects of glucose molecules on montmorillonite interlayer properties. Molecular dynamics simulations revealed re-structuring of the interlayer organization of the adsorptive species. Water-water interactions were disrupted by glucose-water H-bonding interactions. ;Dehydration; of the glucose-populated nanopore led to depletion in the Na solvation shell, which resulted in the accumulation of both Na ions (as inner-sphere complexes) and remaining hydrated water molecules at the mineral surface. This accumulation led to a decrease in both DNa and Dwater. In addition, the reduction in Dglucose as a function of increasing glucose content can be explained by the aggregation of glucose molecules into organic clusters H-bonded to the mineral surface on both walls of the nanopore. Experimental nuclear magnetic resonance and X-ray diffraction data were consistent with the theoretical predictions. Compared to clay interlayers devoid of glucose, increased intensities and new peaks in the 23Na nuclear magnetic resonance spectra confirmed increasing immobilization of Na as a function of increasing glucose content. And, the X-ray diffraction data indicated a reduced collapse of glucose-populated interlayers exposed to decreasing moisture conditions, which led to the maintenance of hydrated clay nanopores. The coupling of theoretical and experimental findings sheds light on the molecular to nanoscale mechanisms that control the enhanced trapping of water molecules and solutes within sugar-enriched clay nanopores.

Probing Interactions at the Nanoscale by Ion Current through Nanopores and Nanovoids

NASA Astrophysics Data System (ADS)

Gamble, Trevor Patrick

Polymer nanopores offer themselves as excellent test beds for study of phenomena that occur on the nano-scale, such as Debye layer formation, surface charge modulation, current saturation, and rectification. Studying ions interactions within the Debye layer, for example, is not possible on the micro-scale, where the pore diameter can be 100 times the size of the zone where interactions of interest occur. However, in our nanopores with an opening diameter less than 10 nm, a slight change of the Debye length can lead to drastic changes of the recorded ion current. Here we present our nanopores' use as a tool to study geometrical and electrochemical properties of porous manganese oxide. There is great value in studying nano-scale properties of this material because of its importance in lithium ion batteries and newly developed nano-architectures within supercapacitors. We electrodeposited manganese oxide wires into our cylindrical nanopores, filling them completely. In this use, nanopores became a template to probe properties of the embedded material such as surface charge, ion selectivity, and porosity. This information was then reported to the Energy Frontier Research Center (EFRC) collaboration, so that other groups can incorporate these recently discovered characteristics into future their nano-architecture design. Additionally, we constructed conical nanopores to study interactions between the surface charges found on the walls and alkali metal ions. In particular we looked at lithium, as it is the electrochemically active ion during charge cycling in EFRC energy storage devices. We attempted to reveal lithium ion's affinity to bind to surface charges. We found this binding led to lowering of the effective surface charge of the pore walls, while also decreasing lithium's ability to move through channels or voids that have charged walls. In connection to manganese oxide, a porous, charged material with voids, information on lithium's interaction with these charges is paramount.

Effect of Graphene with Nanopores on Metal Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hu; Chen, Xianlang; Wang, Lei

Porous graphene, which is a novel type of defective graphene, shows excellent potential as a support material for metal clusters. In this work, the stability and electronic structures of metal clusters (Pd, Ir, Rh) supported on pristine graphene and graphene with different sizes of nanopore were investigated by first-principle density functional theory (DFT) calculations. Thereafter, CO adsorption and oxidation reaction on the Pd-graphene system were chosen to evaluate its catalytic performance. Graphene with nanopore can strongly stabilize the metal clusters and cause a substantial downshift of the d-band center of the metal clusters, thus decreasing CO adsorption. All binding energies,more » d-band centers, and adsorption energies show a linear change with the size of the nanopore: a bigger size of nanopore corresponds to a stronger metal clusters bond to the graphene, lower downshift of the d-band center, and weaker CO adsorption. By using a suitable size nanopore, supported Pd clusters on the graphene will have similar CO and O2 adsorption ability, thus leading to superior CO tolerance. The DFT calculated reaction energy barriers show that graphene with nanopore is a superior catalyst for CO oxidation reaction. These properties can play an important role in instructing graphene-supported metal catalyst preparation to prevent the diffusion or agglomeration of metal clusters and enhance catalytic performance. This work was supported by National Basic Research Program of China (973Program) (2013CB733501), the National Natural Science Foundation of China (NSFC-21176221, 21136001, 21101137, 21306169, and 91334013). D. Mei acknowledges the support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC).« less

Method of producing nanopatterned articles, and articles produced thereby

DOEpatents

Russell, Thomas P; Park, Soojin; Xu, Ting

2013-11-12

A nanopatterned surface is prepared by forming a block copolymer film on a miscut crystalline substrate, annealing the block copolymer film, then reconstructing the surface of the annealed block copolymer film. The method creates a well-ordered array of voids in the block copolymer film that is maintained over a large area. The nanopatterned block copolymer films can be used ina variety of different applications, including the fabrication of high density data storage media.

Hyper-dendritic nanoporous zinc foam anodes, methods of producing the same, and methods for their use

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steingart, Daniel A.; Chamoun, Mylad; Hertzberg, Benjamin

Disclosed are hyper-dendritic nanoporous zinc foam electrodes, viz., anodes, methods of producing the same, and methods for their use in electrochemical cells, especially in rechargeable electrical batteries.

Silver-halide photographic materials based on nanoporous glasses

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Obyknovennaya, I. E.; Gavrilyuk, E. R.; Paramonov, A. A.; Kushnarenko, A. P.

2005-12-01

This paper discusses the results of an investigation of the recording of composite nanoporous photographic materials with a photosensitive composite made from silver halide in gelatin, developed and created at S. I. Vavilov State Optical Institute.

Highly cross-linked nanoporous polymers

DOEpatents

Steckle, Jr., Warren P.; Apen, Paul G.; Mitchell, Michael A.

1998-01-01

Condensation polymerization followed by a supercritical extraction step can be used to obtain highly cross-linked nanoporous polymers with high surface area, controlled pore sizes and rigid structural integrity. The invention polymers are useful for applications requiring separation membranes.